Vinyl terminated macromonomers

ABSTRACT

Polymers produced by a process comprising contacting one or more olefins with a catalyst system comprising an activator and a Salan catalyst disposed on a support.

RELATED APPLICATIONS

This application is a divisional application of U.S. Ser. No.14/059,081, filed Oct. 21, 2013, which claims priority to and thebenefit of provisional application U.S. 61/722,110, filed Nov. 2, 2012,and which is hereby incorporated herein by reference.

NAMES OF PARTIES TO JOINT RESEARCH AGREEMENT

(1) ExxonMobil Chemical Company, a division of ExxonMobil Corporation;(2) Ramot at Tel Aviv University Ltd.

FIELD OF THE INVENTION

This invention relates to supported Salan catalysts, processes utilizingsuch catalysts, and polymers produced thereby.

BACKGROUND OF THE INVENTION

Supported olefin polymerization catalysts are of great use in industry.Hence there is interest in finding new supported catalyst systems thatincrease the commercial usefulness of the catalyst and allow theproduction of polymers having improved properties.

There is a need in the art for new and improved supported catalysts andcatalyst systems to obtain new and improved polyolefins, polymerizationprocesses, and the like. Accordingly, there is a need in the art for newand improved supported catalyst systems for the polymerization ofolefins, in order to achieve specific polymer properties such as vinyltermination.

SUMMARY OF THE INVENTION

The instant disclosure is directed to supported catalyst compounds,supported activators, and catalyst systems comprising such compounds,processes for the preparation of the catalyst compounds and systems, andprocesses for the polymerization of olefins using such supportedcatalyst compounds and systems.

In an embodiment according to the invention, a process comprisescontacting one or more olefins with a catalyst system at a temperature,a pressure, and for a period of time sufficient to produce a polyolefin;the catalyst system comprising an activator and a catalyst compounddisposed on a support, according to Formula I, Formula II, Formula III,or a combination thereof:

Formula I being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof,        or a combination thereof; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;

Formula II being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², and N³ are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical, and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;

Formula III being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹ and N² are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,        independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or two or more of R¹ to R²¹ may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure, or a combination thereof;    -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or R²⁰        comprise fluorine; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

In an embodiment according to the invention, a polyolefin comprises atleast 50 mol % ethylene, the polymer produced by a process comprising:

-   -   contacting one or more olefins with a catalyst system at a        temperature, a pressure, and for a period of time sufficient to        produce a polyolefin, the catalyst system comprising an        activator and a catalyst compound disposed on a support; wherein        the catalyst compound is according to Formula I, Formula II,        Formula III, or a combination thereof:

Formula I being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², N³ and N⁴ are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶,        R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl        radical, a functional group comprising elements from Groups        13-17 of the periodic table of the elements, or two or more of        R¹ to R²⁸ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure, or a combination thereof,        or a combination thereof; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;

Formula II being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹, N², and N³ are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group        comprising elements from Group 13-17 of the periodic table of        the elements, or two or more of R¹ to R²¹ may independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, or a combination thereof; subject to the proviso that        R¹⁹ is not a carbazole or a substituted carbazole radical; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;

Formula III being represented by:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   wherein M is a Group 3, 4, 5 or 6 transition metal;    -   N¹ and N² are nitrogen;    -   O is oxygen;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,        independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or two or more of R¹ to R²¹ may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure, or a combination thereof;    -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or R²⁰        comprise fluorine; and    -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto, the newnumbering scheme for the Periodic Table Groups is used as in Chem. Eng.News, 1985, 63, 27. Therefore, a “Group 4 metal” is an element fromGroup 4 of the Periodic Table.

In the structures depicted throughout this specification and the claims,a solid line indicates a bond, an arrow indicates that the bond may bedative, and each dashed line represents a bond having varying degrees ofcovalency and a varying degree of coordination.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document unless otherwisespecified. For purposes of this disclosure, a hydrocarbyl radical isdefined to be C₁ to C₇₀ radicals, or C₁ to C₂₀ radicals, or C₁ to C₁₀radicals, or C₆ to C₇₀ radicals, or C₆ to C₂₀ radicals, or C₇ to C₂₀radicals that may be linear, branched, or cyclic where appropriate(aromatic or non-aromatic); and includes hydrocarbyl radicalssubstituted with other hydrocarbyl radicals and/or one or morefunctional groups comprising elements from Groups 13-17 of the periodictable of the elements. In addition two or more such hydrocarbyl radicalsmay together form a fused ring system, including partially or fullyhydrogenated fused ring systems, which may include heterocyclicradicals.

For purposes herein, a carbazole or substituted carbazole radical isrepresented by the formula:

wherein each R¹ through R⁸ is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Group13-17 of the periodic table of the elements, or two or more of R¹ to R⁸may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure, or a combination thereof.

The term “substituted” means that a hydrogen atom and/or a carbon atomin the base structure has been replaced with a hydrocarbyl radical,and/or a functional group, and/or a heteroatom or a heteroatomcontaining group. Accordingly, the term hydrocarbyl radical includesheteroatom containing groups. For purposes herein, a heteroatom isdefined as any atom other than carbon and hydrogen. For example, methylcyclopentadiene (Cp) is a Cp group, which is the base structure,substituted with a methyl radical, which may also be referred to as amethyl functional group, ethyl alcohol is an ethyl group, which is thebase structure, substituted with an —OH functional group, and pyridineis a phenyl group having a carbon in the base structure of the benzenering substituted with a nitrogen atom.

For purposes herein, a hydrocarbyl radical may be independently selectedfrom substituted or unsubstituted methyl, ethyl, ethenyl and isomers ofpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl,tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl,eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl,pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl,triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl,nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl,eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl,pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, andtriacontynyl.

For purposes herein, hydrocarbyl radicals may also include isomers ofsaturated, partially unsaturated and aromatic cyclic structures whereinthe radical may additionally be subjected to the types of substitutionsdescribed above. The term “aryl”, “aryl radical”, and/or “aryl group”refers to aromatic cyclic structures, which may be substituted withhydrocarbyl radicals and/or functional groups as defined herein.Examples of aryl radicals include: acenaphthenyl, acenaphthylenyl,acridinyl, anthracenyl, benzanthracenyls, benzimidazolyl,benzisoxazolyl, benzofluoranthenyls, benzofuranyl, benzoperylenyls,benzopyrenyls, benzothiazolyl, benzothiophenyls, benzoxazolyl, benzyl,carbazolyl, carbolinyl, chrysenyl, cinnolinyl, coronenyl, cyclohexyl,cyclohexenyl, methylcyclohexyl, dibenzoanthracenyls, fluoranthenyl,fluorenyl, furanyl, imidazolyl, indazolyl, indenopyrenyls, indolyl,indolinyl, isobenzofuranyl, isoindolyl, isoquinolinyl, isoxazolyl,methyl benzyl, methylphenyl, naphthyl, oxazolyl, phenanthrenyl, phenyl,purinyl, pyrazinyl, pyrazolyl, pyrenyl, pyridazinyl, pyridinyl,pyrimidinyl, pyrrolyl, quinazolinyl, quinolonyl, quinoxalinyl,thiazolyl, thiophenyl, and the like.

It is to be understood that for purposes herein, when a radical islisted, it indicates that the base structure of the radical (the radicaltype) and all other radicals formed when that radical is subjected tothe substitutions defined above. Alkyl, alkenyl, and alkynyl radicalslisted include all isomers including where appropriate cyclic isomers,for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl,tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls);pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 1-ethylpropyl, and nevopentyl (and analogous substitutedcyclobutyls and cyclopropyls); butenyl includes E and Z forms of1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl,1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (andcyclobutenyls and cyclopropenyls). Cyclic compounds having substitutionsinclude all isomer forms, for example, methylphenyl would includeortho-methylphenyl, meta-methylphenyl and para-methylphenyl;dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl,2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and3,5-dimethylphenyl.

Likewise the terms “functional group”, “group” and “substituent” arealso used interchangeably throughout this document unless otherwisespecified. For purposes herein, a functional group includes both organicand inorganic radicals or moieties comprising elements from Groups 13,14, 15, 16, and 17 of the periodic table of elements. Suitablefunctional groups may include hydrocarbyl radicals, e.g., alkylradicals, alkene radicals, aryl radicals, and/or halogen (Cl, Br, I, F),O, S, Se, Te, NR*_(x), OR*, SeR*, TeR*, PR*_(x), AsR*_(x), SbR*_(x),SR*, BR*_(x), SiR*_(x), GeR*_(x), SnR*_(x), PbR*_(x), and/or the like,wherein R is a C₁ to C₂₀ hydrocarbyl as defined above and wherein x isthe appropriate integer to provide an electron neutral moiety. Otherexamples of functional groups include those typically referred to asamines, imides, amides, ethers, alcohols (hydroxides), sulfides,sulfates, phosphides, halides, phosphonates, alkoxides, esters,carboxylates, aldehydes, and the like.

For purposes herein, a supported catalyst and/or activator refers to acatalyst compound, an activator, or a combination thereof located on, inor in communication with a support wherein the activator, the catalystcompound, or a combination thereof are deposited on, vaporized with,bonded to, incorporated within, adsorbed or absorbed in, adsorbed orabsorbed on, the support.

Where reference is made herein to two substituents joining together toform a cyclic or polycyclic ring structure, one substituent is directlybridged to another substituent when the two substituents together formonly a covalent bond containing no atoms, i.e., the substituents are notdirectly bridged if they together comprise a bridge of at least oneatom.

For purposes herein an “olefin,” alternatively referred to as “alkene,”is a linear, branched, or cyclic compound comprising carbon and hydrogenhaving at least one double bond. For purposes of this specification andthe claims appended thereto, when a polymer or copolymer is referred toas comprising an olefin, the olefin present in such polymer or copolymeris the polymerized form of the olefin. For example, when a copolymer issaid to have an “ethylene” content of 35 wt % to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer.

For purposes herein a “polymer” has two or more of the same or different“mer” units. A “homopolymer” is a polymer having mer units that are thesame. A “copolymer” is a polymer having two or more mer units that aredifferent from each other. A “terpolymer” is a polymer having three merunits that are different from each other. “Different” in reference tomer units indicates that the mer units differ from each other by atleast one atom or are different isomerically. Accordingly, thedefinition of copolymer, as used herein, includes terpolymers and thelike. An oligomer is typically a polymer having a low molecular weight,such as an Mn of less than 25,000 g/mol, or in an embodiment accordingto the invention, less than 2,500 g/mol, or a low number of mer units,such as 75 mer units or less. An “ethylene polymer” or “ethylenecopolymer” is a polymer or copolymer comprising at least 50 mole %ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer comprising at least 50 mole % propylenederived units, and so on.

For the purposes of this disclosure, the term “α-olefin” includes C₂-C₂₂olefins. Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.Non-limiting examples of cyclic olefins and diolefins includecyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene,cyclooctene, cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

The terms “catalyst”, “catalyst compound”, and “transition metalcompound” are defined to mean a compound capable of initiatingpolymerization catalysis under the appropriate conditions. In thedescription herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, or a transition metal compound, andthese terms are used interchangeably. A catalyst compound may be used byitself to initiate catalysis or may be used in combination with anactivator to initiate catalysis. When the catalyst compound is combinedwith an activator to initiate catalysis, the catalyst compound is oftenreferred to as a pre-catalyst or catalyst precursor. A “catalyst system”is combination of at least one catalyst compound, at least oneactivator, an optional co-activator, and an optional support material,where the system can polymerize monomers to polymer. For the purposes ofthis invention and the claims thereto, when catalyst systems aredescribed as comprising neutral stable forms of the components it iswell understood by one of ordinary skill in the art that the ionic formof the component is the form that reacts with the monomers to producepolymers.

For purposes herein the term “catalyst productivity” is a measure of howmany grams of polymer (P) are produced using a polymerization catalystcomprising W grams of catalyst (cat), over a period of time of T hours;and may be expressed by the following formula: P/(T×W) and expressed inunits of gPgcat⁻¹hr⁻¹. Conversion is the amount of monomer that isconverted to polymer product, and is reported as mol % and is calculatedbased on the polymer yield and the amount of monomer fed into thereactor. Catalyst activity is a measure of how active the catalyst isand is reported as the mass of product polymer (P) produced per mole ofcatalyst (cat) used (kg P/mol cat).

An “anionic ligand” is a negatively charged ligand which donates one ormore pairs of electrons to a metal ion. A “neutral donor ligand” is aneutrally charged ligand which donates one or more pairs of electrons toa metal ion.

A scavenger is a compound that is typically added to facilitateoligomerization or polymerization by scavenging impurities. Somescavengers may also act as activators and may be referred to asco-activators. A co-activator, that is not a scavenger, may also be usedin conjunction with an activator in order to form an active catalyst. Inan embodiment according to the invention, a co-activator can bepre-mixed with the catalyst compound to form an alkylated catalystcompound.

A propylene polymer is a polymer having at least 50 mol % of propylene.As used herein, Mn is number average molecular weight as determined byproton nuclear magnetic resonance spectroscopy (¹H NMR) unless statedotherwise, Mw is weight average molecular weight determined by gelpermeation chromatography (GPC), and Mz is z average molecular weightdetermined by GPC, wt % is weight percent, and mol % is mole percent. Inthe alternative, Mw and Mn may be determined by gas chromatography (GC)for polymers having a kinematic viscosity at 100° C. as determinedaccording to ASTM D445 (KV100) less than 10 cSt, and by GPC for KV100 of10 cSt or higher. Molecular weight distribution (MWD) is defined to beMw divided by Mn. Unless otherwise noted, all molecular weight units,e.g., Mw, Mn, Mz, are g/mol.

The following abbreviations may be used through this specification: Meis methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl,n-Pr is normal propyl, Bu is butyl, iso-butyl is isobutyl, sec-butylrefers to secondary butyl, tert-butyl, refers to tertiary butyl, n-butylis normal butyl, pMe is para-methyl, Bn is benzyl, THF istetrahydrofuran, Mes is mesityl, also known as 1,3,5-trimethylbenzene,Tol is toluene, TMS is trimethylsilyl, TIBAL is triisobutylaluminum,TNOAL is triisobutyl n-octylaluminum, MAO is methylalumoxane, MOMO ismethoxymethoxy (also referred to as methoxymethyl ether), N is nitrogen(including that N¹, N², N³ and N⁴ are nitrogen) and O is oxygen.

For purposes herein, RT is room temperature, which is defined as 25° C.unless otherwise specified. All percentages are weight percent (wt %)unless otherwise specified.

In the description herein, the Salan catalyst may be described as acatalyst precursor, a pre-catalyst compound, Salan catalyst compound ora transition metal compound, and these terms are used interchangeably.

Catalyst Compounds

In an embodiment according to the invention, the catalyst comprisesGroup 3, 4, 5 and/or 6 disubstituted compounds supported by atetradentate di-anionic Salan ligand, useful to polymerize olefinsand/or α-olefins to produce polyolefins and/or poly(α-olefins). In anembodiment according to the invention, the catalyst compounds arerepresented by the following structure:

-   wherein each solid line represents a covalent bond and each dashed    line represents a bond having varying degrees of covalency and a    varying degree of coordination;-   N¹, N², N³ and N⁴ are nitrogen;-   O is oxygen;-   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to each    oxygen atom, and bonded with varying degrees of covalency and    coordination to each of nitrogen atoms N¹ and N²;-   each of X¹ and X² is, independently, a univalent C₁ to C₂₀    hydrocarbyl radical, a functional group comprising elements from    Groups 13-17 of the periodic table of the elements, or X¹ and X²    join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure, provided however when M is trivalent X² is not present;-   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷ and    R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl, a    functional group comprising elements from Group 13-17 of the    periodic table of the elements, or two or more of R¹ to R²⁸ may    independently join together to form a C₄ to C₆₂ cyclic or polycyclic    ring structure, or a combination thereof; and-   Y is a divalent hydrocarbyl radical covalently bonded to and    bridging between both of the nitrogen atoms N¹ and N². In an    embodiment according to the invention, two or more of R¹ to R²⁸ may    independently join together to form a C₄ to C₆₂ cyclic or polycyclic    ring structure.

In an embodiment according to the invention, the catalyst compound isrepresented by the formula:

-   wherein A is represented by the formula, attached to the nitrogen    atom, labeled N³ of the carbazole ring:

-   wherein A′ is represented by the formula, attached to the nitrogen    atom labeled N⁴ of the carbazole ring:

-   wherein M is a Group 3, 4, 5 or 6 transition metal;-   each of X¹ and X² is, independently, a univalent C₁ to C₂₀    hydrocarbyl radical, a functional group comprising elements from    Groups 13-17 of the periodic table of the elements, or X¹ and X²    join together to form a C₄ to C₆₂ cyclic or polycyclic ring    structure, provided however when M is trivalent X² is not present;-   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,    R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and    R²⁸ is, independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a    functional group comprising elements from Group 13-17 of the    periodic table of the elements, or two or more of R¹ to R²⁸ may    independently join together to form a C₄ to C₆₂ cyclic or polycyclic    ring structure, or a combination thereof; and-   Y and Z form a divalent C₁ to C₂₀ hydrocarbyl radical. In an    embodiment according to the invention, Y and Z are identical. In an    embodiment according to the invention, Y and Z are different.

In an embodiment according to the invention, M is a Group 4 metal, or Mis Hf, Ti and/or Zr, or M is Hf or Zr. In an embodiment according to theinvention, each of X¹ and X² is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, and alkoxides having from 1 to 20 carbon atoms,sulfides, phosphides, halides, amines, phosphines, ethers, andcombinations thereof.

In an embodiment according to the invention, X¹ and X² together form apart of a fused ring or a ring system having from 4 to 62 carbon atoms.

In an embodiment according to the invention, each of X¹ and X² isindependently selected from the group consisting of halides, alkylradicals having from 1 to 7 carbon atoms, benzyl radicals, or acombination thereof.

In an embodiment according to the invention, Y is a divalent C₁-C₄₀hydrocarbyl radical comprising a portion that comprises a linkerbackbone comprising from 1 to 18 carbon atoms linking or bridgingbetween nitrogen atoms N¹ and N². In an embodiment according to theinvention, Y is a C₁-C₄₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*), N or N(R*), wherein each R* isindependently a C₁-C₁₈ hydrocarbyl. In an embodiment according to theinvention, Y is selected from the group consisting of ethylene(—CH₂CH₂—) and 1,2-cyclohexylene, and/or —CH₂CH₂CH₂— derived frompropylene. In an embodiment according to the invention, Y is —CH₂CH₂CH₂—derived from propylene.

In an embodiment according to the invention, each of X¹ and X² is,independently, a halogen or a C₁ to C₇ hydrocarbyl radical.

In an embodiment according to the invention, each of X¹ and X² is abenzyl radical. In an embodiment according to the invention, each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ is,independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl radical,or a C₁ to C₁₀ hydrocarbyl radical. In an embodiment according to theinvention, one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,R²⁶, R²⁷, and R²⁸ is a methyl radical, a fluoride, or a combinationthereof.

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹ and R¹⁴ are methyl radicals; R² through R¹³ and R¹⁵through R²⁸ are hydrogen; and Y is ethylene (—CH₂CH₂—).

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals; R², R³, R⁵through R¹³, R¹⁵, R¹⁶ and R¹⁸ through R²⁸ are hydrogen; and Y isethylene (—CH₂CH₂—).

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹ and R¹⁴ are methyl radicals; R⁴ and R¹⁷ are fluoro(F) functional groups; R², R³, R⁵ through R¹³, R¹⁵, R¹⁶ and R¹⁸ throughR²⁸ are hydrogen; and Y is ethylene —CH₂CH₂—).

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹, R⁴, R¹⁴, and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹,and R²⁴ are tert-butyl radicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³,R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²², R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen;and Y is ethylene (—CH₂CH₂—).

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals; R⁸, R¹¹, R²¹and R²⁴ are mesityl radicals; R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³,R¹⁵, R¹⁶, R¹⁸, R¹⁹, R²⁰, R²², R²³, R²⁵, R²⁶, R²⁷, and R²⁸ are hydrogen;and Y is ethylene (—CH₂CH₂—).

In an embodiment according to the invention, the catalyst comprisesGroup 3, 4, 5 and/or 6 disubstituted compounds supported by atetradentate di-anionic Salan ligand, useful to polymerize olefinsand/or α-olefins to produce polyolefins and/or poly(α-olefins). In anembodiment according to the invention, the catalyst compounds arerepresented by the following structure:

-   -   wherein each solid line represents a covalent bond and each        dashed line represents a bond having varying degrees of        covalency and a varying degree of coordination;    -   N¹, N², and N³ are nitrogen;    -   O is oxygen;    -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹ to R²¹ may independently join together to        form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a        combination thereof, subject to the proviso that R¹⁹ is not a        carbazole or a substituted carbazole radical; and    -   Y is a divalent hydrocarbyl radical covalently bonded to and        bridging between both of the nitrogen atoms N¹ and N². In an        embodiment according to the invention, two or more of R¹ to R²¹        may independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure. Accordingly, the instant disclosure        in one embodiment is directed to non-symmetrical Salan        catalysts. The Salan catalysts disclosed in this embodiment are        devoid of a symmetry element, having a non-symmetric or        non-palindromic structure. By non-symmetric, it is meant that        the two phenol moieties of the Salan compound are substituted        differently when comparing the substitutions of one phenol,        which comprises a carbazole or substituted carbazole radical,        and the other phenol which may comprise a differently        substituted carbazole, or as is shown in the above structure        does not comprise a carbazole or a substituted carbazole radical        at position R¹⁹ (i.e., subject to the proviso that R¹⁹ is not a        carbazole or a substituted carbazole radical).

In an embodiment according to the invention, a catalyst compound isrepresented by the structure

wherein A is represented by the structure attached at the carbazolenitrogen atom:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination;

-   -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is independently, a        hydrogen, a C₁-C₄₀ hydrocarbyl, a functional group comprising        elements from Group 13-17 of the periodic table of the elements,        or two or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹,        R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ may        independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure, or a combination thereof, subject to        the proviso that R¹⁹ is not identical to A; and    -   Y and Z form a divalent hydrocarbyl radical covalently bonded to        and bridging between both of the nitrogen atoms N¹ and N². In an        embodiment according to the invention, Y is identical to Z. In        an embodiment according to the invention, Y is different to Z.        In an embodiment according to the invention, two or more of R¹        to R²¹ may independently join together to form a C₄ to C₆₂        cyclic or polycyclic ring structure.

In an embodiment according to the invention, M is a Group 4 metal, or Mis Hf, Ti and/or Zr, or M is Hf or Zr. In an embodiment according to theinvention, each of X¹ and X² is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, and alkoxides having from 1 to 20 carbon atoms,sulfides, phosphides, halides, amines, phosphines, ethers, andcombinations thereof.

In an embodiment according to the invention, X¹ and X² together form apart of a fused ring or a ring system having from 4 to 62 carbon atoms.

In an embodiment according to the invention, each of X¹ and X² isindependently selected from the group consisting of halides, alkylradicals having from 1 to 7 carbon atoms, benzyl radicals, or acombination thereof.

In an embodiment according to the invention, Y is a divalent C₁-C₄₀hydrocarbyl radical comprising a portion that comprises a linkerbackbone comprising from 1 to 18 carbon atoms linking or bridgingbetween nitrogen atoms N¹ and N². In an embodiment according to theinvention, Y is a C₁-C₄₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*), N or N(R*), wherein each R* isindependently a C₁-C₁₈ hydrocarbyl. In an embodiment according to theinvention, Y is selected from the group consisting of ethylene(—CH₂CH₂—) and 1,2-cyclohexylene, and/or —CH₂CH₂CH₂— derived frompropylene. In an embodiment according to the invention, Y is —CH₂CH₂CH₂—derived from propylene.

In an embodiment according to the invention, each of X¹ and X² is,independently, a halogen or a C₁ to C₇ hydrocarbyl radical.

In an embodiment according to the invention, each of X¹ and X² is abenzyl radical. In an embodiment according to the invention, each R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, hydrogen, a halogen, or a C₁to C₃₀ hydrocarbyl radical, or a C₁ to C₁₀ hydrocarbyl radical, subjectto the proviso that R¹⁹ is not a carbazole or a substituted carbazoleradical. In an embodiment according to the invention, one or more of R¹,R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷,R¹⁸, R¹⁹, R²⁰, and R²¹ is a methyl radical, a bromine, an adamantylradical, or a combination thereof.

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl; R¹ and R¹⁴ are methyl; R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ andR²¹ are hydrogen; R¹⁷ and R¹⁹ are bromine; and Y is —CH₂CH₂—.

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl; R¹, R¹⁴ and R¹⁷ are methyl; R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰and R²¹ are hydrogen; R¹⁹ is 1-adamantyl; and Y is —CH₂CH₂—.

In an embodiment according to the invention, M is Hf; X¹ and X² arebenzyl; R¹ and R¹⁴ are methyl; R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ andR²¹ are hydrogen; R¹⁷ is methyl; R¹⁹ is 1-adamantyl; and Y is —CH₂CH₂—.

In an embodiment according to the invention, the catalyst comprises acompound represented by the formula:

-   -   where each solid line represents a covalent bond and each dashed        line represents a bond having varying degrees of covalency and a        varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀        hydrocarbyl radical, a functional group comprising elements from        Groups 13-17 of the periodic table of the elements, or X¹ and X²        join together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure, provided however when M is trivalent X² is not        present;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,        independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or a combination thereof;    -   wherein at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        or R²⁰ comprise fluorine; and    -   Y is a divalent hydrocarbyl radical covalently bonded to and        bridging between both of the nitrogen atoms N¹ and N².

In an embodiment according to the invention, two or more of R¹ to R²²may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure. Accordingly, the instant disclosure is directed tonon-symmetrical Salan catalysts. The Salan catalysts disclosed hereinare at least partially fluorinated, and may include perfluorinated orpartially perfluorinated aromatic ring systems as substituents.

In an embodiment according to the invention, the catalyst compound isrepresented by the following formula:

-   -   wherein substituent A is represented by the following formula,        attached to the benzene ring:

-   -   wherein substituent A′ is represented by the following formula        attached to the benzene ring:

-   -   where each solid line represents a covalent bond and each dashed        line represents a bond having varying degrees of covalency and a        varying degree of coordination;    -   M is a Group 3, 4, 5 or 6 transition metal covalently bonded to        each oxygen atom, and bonded with varying degrees of covalency        and coordination to each of nitrogen atoms N¹ and N²;    -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,        R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,        independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a        functional group comprising elements from Group 13-17 of the        periodic table of the elements, or a combination thereof;    -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or R²⁰        comprise fluorine; and    -   Y and Z form divalent hydrocarbyl radical covalently bonded to        and bridging between both of the nitrogen atoms N¹ and N². In an        embodiment according to the invention, two or more of R¹ to R²²        may independently join together to form a C₄ to C₆₂ cyclic or        polycyclic ring structure. In an embodiment according to the        invention, Y is identical to Z. In an embodiment according to        the invention, Y is different than Z.

For purposes herein, a perfluorinated ring is defined as a ring systemwherein each of the available hydrogen atoms are substituted with afluorine atom, also referred to as a fluoride.

In an embodiment according to the invention, M is a Group 4 metal, or Mis Hf, Ti and/or Zr, or M is Ti or Zr. In an embodiment according to theinvention, each of X¹ and X² is independently selected from the groupconsisting of hydrocarbyl radicals having from 1 to 20 carbon atoms,hydrides, amides, and alkoxides having from 1 to 20 carbon atoms,sulfides, phosphides, halides, amines, phosphines, ethers, andcombinations thereof.

In an embodiment according to the invention, X¹ and X² together form apart of a fused ring or a ring system having from 4 to 62 carbon atoms.

In an embodiment according to the invention, each of X¹ and X² isindependently selected from the group consisting of halides, alkylradicals having from 1 to 7 carbon atoms, benzyl radicals, or acombination thereof.

In an embodiment according to the invention, Y is a divalent C₁-C₄₀hydrocarbyl radical comprising a portion that comprises a linkerbackbone comprising from 1 to 18 carbon atoms linking or bridgingbetween nitrogen atoms N¹ and N². In an embodiment according to theinvention, Y is a C₁-C₄₀ hydrocarbyl radical comprising a portion thatcomprises a linker backbone comprising from 1 to 18 carbon atoms linkingthe nitrogen atoms N¹ and N² wherein the hydrocarbyl comprises O, S,S(O), S(O)₂, Si(R*)₂, P(R*), N or N(R*), wherein each R* isindependently a C₁-C₁₈ hydrocarbyl. In an embodiment according to theinvention, Y is selected from the group consisting of ethylene(—CH₂CH₂—) and 1,2-cyclohexylene, and/or —CH₂CH₂CH₂— derived frompropylene. In an embodiment according to the invention, Y is —CH₂CH₂CH₂—derived from propylene.

In an embodiment according to the invention, each of X¹ and X² is,independently, a halogen or a C₁ to C₇ hydrocarbyl radical. In anembodiment according to the invention, each of X¹ and X² is a benzylradical.

In an embodiment according to the invention, each R¹, R², R³, R⁴, R⁵,R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,R²¹, and R²² is, independently, hydrogen, a halogen, or a C₁ to C₃₀hydrocarbyl radical, or a C₁ to C₁₀ hydrocarbyl radical.

In an embodiment according to the invention, one or more of R¹, R², R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,R¹⁹, R²⁰, R²¹, and R²² is a methyl radical, or a fluoride, which mayalso be referred to as a fluorine or a fluorine functional group.

In an embodiment according to the invention, M is Ti; X¹ and X² arebenzyl radicals; R¹ and R¹¹ are methyl radicals; R², R³, R⁵, R¹², R¹³,R¹⁵, R²¹ and R²² are hydrogen; R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷,R¹⁸, R¹⁹, and R²⁰ are fluorine; and Y is —CH₂CH₂—.

In an embodiment according to the invention, M is Ti; X¹ and X² arebenzyl radicals; R¹, R⁴, R¹¹, and R¹⁴ are methyl radicals; R², R³, R⁵,R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen; R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷,R¹⁸, R¹⁹, and R²⁰ are fluorine; and Y is —CH₂CH₂—.

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹ and R¹¹ are methyl radicals; R², R³, R⁵, R¹², R¹³,R¹⁵, R²¹ and R²² are hydrogen; R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷,R¹⁸, R¹⁹, and R²⁰ are fluorine; and Y is —CH₂CH₂—.

In an embodiment according to the invention, M is Zr; X¹ and X² arebenzyl radicals; R¹, R⁴, R¹¹, and R¹⁴ are methyl radicals; R², R³, R⁵,R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen; R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷,R¹⁸, R¹⁹, and R²⁰ are fluorine; and Y is —CH₂CH₂—.

In an embodiment according to the invention, two or more differentcatalyst compounds are present in the catalyst system used herein. In anembodiment according to the invention, two or more different catalystcompounds are present in the reaction zone where the process(es)described herein occur. When two transition metal compound basedcatalysts are used in one reactor as a mixed catalyst system, the twotransition metal compounds are chosen such that the two are compatible.Compatible catalysts are those catalysts having similar kinetics oftermination and insertion of monomer and comonomer(s) and/or do notdetrimentally interact with each other. For purposes herein, the term“incompatible catalysts” refers to and means catalysts that satisfy oneor more of the following:

1) those catalysts that when present together reduce the activity of atleast one of the catalysts by greater than 50%;

2) those catalysts that under the same reactive conditions producepolymers such that one of the polymers has a molecular weight that ismore than twice the molecular weight of the other polymer; and

3) those catalysts that differ in comonomer incorporation or reactivityratio under the same conditions by more than about 30%. A simplescreening method such as by ¹H or ¹³C NMR, known to those of ordinaryskill in the art, can be used to determine which transition metalcompounds are compatible. In an embodiment according to the invention,the catalyst systems use the same activator for the catalyst compounds.In an embodiment according to the invention, two or more differentactivators, such as a non-coordinating anion activator and an alumoxane,can be used in combination. If one or more catalyst compounds contain anX¹ or X² ligand which is not a hydride, or a hydrocarbyl, then in anembodiment according to the invention, the alumoxane is contacted withthe catalyst compounds prior to addition of the non-coordinating anionactivator.

In an embodiment according to the invention, when two transition metalcompounds (pre-catalysts) are utilized, they may be used in any ratio.In an embodiment according to the invention, a molar ratio of a firsttransition metal compound (A) to a second transition metal compound (B)will fall within the range of (A:B) 1:1000 to 1000:1, or 1:100 to 500:1,or 1:10 to 200:1, or 1:1 to 100:1, or 1:1 to 75:1, or 5:1 to 50:1. Theparticular ratio chosen will depend on the exact pre-catalysts chosen,the method of activation, and the end product desired. In an embodimentaccording to the invention, when using two pre-catalysts, where both areactivated with the same activator, useful mole percents, based upon thetotal moles of the pre-catalysts, are 10:90 to 0.1:99, or 25:75 to 99:1,or 50:50 to 99.5:0.5, or 50:50 to 99:1, or 75:25 to 99:1, or 90:10 to99:1.

Methods to Prepare the Catalyst Compounds

In embodiments the symmetric transition metal compounds may be preparedby two general synthetic routes. The parent Salan ligands are preparedby a one-step Mannich reaction from the parent phenol (Reaction A) or bya two-step imine-condensation/alkylation procedure if thesalicylaldehyde is used (Reaction B). The ligand is then converted intothe metal dibenzyl catalyst precursor by reaction with the metaltetra-aryl starting material, e.g., tetrabenzyl, to yield the finishedcomplex (Reaction C).

Asymmetric transition metal compounds may be prepared by a step-wisesynthetic route. The parent Salan ligands may be prepared by reaction ofthe salicylaldehyde with the diamine, followed by reduction with NaBH₄.The asymmetric ligand may then be formed by an HBr elimination reactionwith a bromomethylphenol (Reaction D). The ligand may then be convertedinto the metal dibenzyl catalyst precursor by reaction with the metaltetrabenzyl starting material to yield the finished complex (ReactionE).

Activators

The terms “cocatalyst” and “activator” are used interchangeably todescribe activators and are defined to be any compound which canactivate any one of the catalyst compounds described above by convertingthe neutral catalyst compound to a catalytically active catalystcompound cation. Non-limiting activators, for example, includealumoxanes, aluminum alkyls, ionizing activators, which may be neutralor ionic, and conventional-type cocatalysts. Activators may includealumoxane compounds, modified alumoxane compounds, and ionizing anionprecursor compounds that abstract a reactive, σ-bound, metal ligandmaking the metal complex cationic and providing a charge-balancingnoncoordinating or weakly coordinating anion.

In one embodiment, alumoxane activators are utilized as an activator inthe catalyst composition. Alumoxanes are generally oligomeric compoundscontaining —Al(R¹)—O— sub-units, where R¹ is an alkyl radical. Examplesof alumoxanes include methylalumoxane (MAO), modified methylalumoxane(MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes andmodified alkylalumoxanes are suitable as catalyst activators,particularly when the catalyst precursor compound comprises anabstractable ligand which is an alkyl, halide, alkoxide or amide.Mixtures of different alumoxanes and modified alumoxanes may also beused. In an embodiment according to the invention, visually clearmethylalumoxane may be used. A cloudy or gelled alumoxane can befiltered to produce a clear solution or clear alumoxane can be decantedfrom the cloudy solution. A useful alumoxane is a modified methylalumoxane (MMAO) described in U.S. Pat. No. 5,041,584 and/orcommercially available from Akzo Chemicals, Inc. under the tradedesignation Modified Methylalumoxane type 3A. Solid alumoxanes may alsobe used.

In an embodiment according to the invention, the activator is aTMA-depleted activator (where TMA is the abbreviation fortrimethylaluminum). The inventors have advantageously found that using aTMA-depleted alkyl alumoxane contributes to producing a polymer withhigher allyl chain ends. Commercial alumoxanes, such as methylalumoxane(MAO) and isobutylalumoxane, often tend to comprise some residualstarting material as an impurity. For example, one common method ofmaking MAO is the hydrolysis of trimethylaluminum (TMA). Suchhydrolysis, however, tends to leave residual TMA in the MAO which mayhave negative effects on polymerization. Any methods known in the art toremove TMA may be used. In an embodiment according to the invention, forexample, to produce a TMA-depleted activator, a solution of alumoxane(such as methylalumoxane), for example, 30 wt % in toluene may bediluted in toluene and the aluminum alkyl (such as TMA in the case ofMAO) is removed from the solution, for example, by combination withtrimethylphenol and filtration of the solid. In an embodiment accordingto the invention, the TMA-depleted activator comprises from about 1 wt %to about 14 wt % trimethylaluminum, or less than 13 wt %, or less than12 wt %, or less than 10 wt %, or less than 5 wt %, or 0 wt %, and/or,greater than 0 wt %, or greater than 1 wt %.

When the activator is an alumoxane (modified or unmodified), in anembodiment according to the invention, the maximum amount of activatoris typically about 5000-fold molar excess Al/M over the catalystcompound (per metal catalytic site). In an embodiment according to theinvention, the minimum activator-to-catalyst-compound determinedaccording to molar concentration of the transition metal M is typicallyabout 1 mole aluminum or less to mole of transition metal M. In anembodiment according to the invention, the activator comprises alumoxaneand the alumoxane is present at a ratio of 1 mole aluminum or more tomole of catalyst compound. In an embodiment according to the invention,the minimum activator-to-catalyst-compound molar ratio is typically a1:1 molar ratio. Other examples of Al:M ranges include from 1:1 to500:1, or from 1:1 to 200:1, or from 1:1 to 100:1, or from 1:1 to 50:1.

In an embodiment according to the invention, little or no alumoxane(i.e., less than 0.001 wt %) is used in the polymerization processesdescribed herein. In an embodiment according to the invention, alumoxaneis present at 0.00 mole %, or the alumoxane is present at a molar ratioof aluminum to catalyst compound transition metal less than 500:1, orless than 300:1, or less than 100:1, or less than 1:1.

Scavengers or Co-Activators

In an embodiment according to the invention, the catalyst system mayfurther include scavengers and/or co-activators. Suitable aluminum alkylor organoaluminum compounds which may be utilized as scavengers orco-activators include, for example, trimethylaluminum, triethylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and thelike. Other oxophilic species such as diethyl zinc may be used. In anembodiment according to the invention, the scavengers and/orco-activators are present at less than 14 wt %, or from 0.1 to 10 wt %,or from 0.5 to 7 wt %, by weight of the catalyst system.

Supports

In an embodiment according to the invention, the catalyst system maycomprise an inert support material. In an embodiment according to theinvention, the support material comprises a porous support material, forexample, talc, and/or inorganic oxides. Other suitable support materialsinclude zeolites, clays, organoclays, or any other organic or inorganicsupport material and the like, or mixtures thereof.

In an embodiment according to the invention, the support material is aninorganic oxide in a finely divided form. Suitable inorganic oxidematerials for use in catalyst systems herein include Groups 2, 4, 13,and 14 metal oxides, such as silica, alumina, and mixtures thereof.Other inorganic oxides that may be employed either alone or incombination with the silica, and/or alumina include magnesia, titania,zirconia, montmorillonite, phyllosilicate, and/or the like, as well ascombinations of these support materials including silica-chromium,silica-alumina, silica-titania, and the like. In an embodiment accordingto the invention, the support materials include Al₂O₃, ZrO₂, SiO₂,SiO₂/Al₂O₃, and combinations thereof. Other suitable support materialsinclude finely divided functionalized polyolefins, such as finelydivided polyethylene.

In an embodiment according to the invention, the support material mayhave a surface area in the range of from about 10 to about 700 m²/g,pore volume in the range of from about 0.1 to about 4.0 cc/g and averageparticle size in the range of from about 5 to about 500 μm, or thesurface area of the support material is in the range of from about 50 toabout 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g andaverage particle size of from about 10 to about 200 μm. In an embodimentaccording to the invention, a majority portion of the surface area ofthe support material is in the range is from about 100 to about 400m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particlesize is from about 5 to about 100 μm. In an embodiment according to theinvention, the average pore size of the support material is in the rangeof from 10 to 1000 Å, or 50 to about 500 Å, or 75 to about 350 Å. In anembodiment according to the invention, the support material is a highsurface area, amorphous silica having a surface area greater than orequal to about 300 m²/g, and/or a pore volume of 1.65 cm³/gm. Suitablesilicas are marketed under the tradenames of Davison 952 or Davison 955by the Davison Chemical Division of W.R. Grace and Company. In anembodiment according to the invention, the support may comprise Davison948.

In an embodiment according to the invention, the support material shouldbe essentially dry, that is, essentially free of absorbed water. Dryingof the support material can be effected by heating or calcining at about100° C. to about 1000° C., or at a temperature of at least about 400°C., or 500° C., or 600° C. When the support material is silica, it isheated to at least 200° C., or about 200° C. to about 850° C., or atleast 600° C. for a time of about 1 minute to about 100 hours, or fromabout 12 hours to about 72 hours, or from about 24 hours to about 60hours. In an embodiment according to the invention, the calcined supportmaterial must have at least some reactive hydroxyl (OH) groups toproduce supported catalyst systems according to the instant disclosure.

In an embodiment according to the invention, the calcined supportmaterial is contacted with at least one polymerization catalystcomprising at least one catalyst compound and an activator. In anembodiment according to the invention, the support material, havingreactive surface groups, typically hydroxyl groups, is slurried in anon-polar solvent and the resulting slurry is contacted with a solutionof a catalyst compound and an activator. In an embodiment according tothe invention, the slurry of the support material is first contactedwith the activator for a period of time in the range of from about 0.5hours to about 24 hours, or from about 2 hours to about 16 hours, orfrom about 4 hours to about 8 hours. The solution of the catalystcompound is then contacted with the isolated support/activator. In anembodiment according to the invention, the supported catalyst system isgenerated in situ. In an alternate embodiment, the slurry of the supportmaterial is first contacted with the catalyst compound for a period oftime in the range of from about 0.5 hours to about 24 hours, or fromabout 2 hours to about 16 hours, or from about 4 hours to about 8 hours.The slurry of the supported catalyst compound is then contacted with theactivator solution.

In an embodiment according to the invention, the mixture of thecatalyst, activator and support is heated to about 0° C. to about 70°C., or to about 23° C. to about 60° C., or to room temperature. Contacttimes typically range from about 0.5 hours to about 24 hours, or fromabout 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, i.e., the activator and the catalyst compound are at leastpartially soluble and which are liquid at reaction temperatures.Suitable non-polar solvents include alkanes, such as isopentane, hexane,n-heptane, octane, nonane, and decane, although a variety of othermaterials including cycloalkanes, such as cyclohexane, aromatics, suchas benzene, toluene, and ethylbenzene, may also be employed.

In an embodiment according to the invention, the activator, the catalystcompound, or a combination thereof is supported by contacting theactivator, the catalyst compound, or both with a support to form asupported activator, supported catalyst, or a combination thereof,wherein the activator, the catalyst compound, or a combination thereofare deposited on, vaporized with, bonded to, incorporated within,adsorbed or absorbed in, or on, the support.

In an embodiment according to the invention, the catalyst compounds,activators and/or catalyst systems disclosed herein may be combined withone or more support materials or carriers. For example, in an embodimentaccording to the invention, the activator is contacted with a support toform a supported activator wherein the activator is deposited on,contacted with, vaporized with, bonded to, or incorporated within,adsorbed or absorbed in, or on, a support or carrier.

In an embodiment according to the invention, the catalyst, theactivator, or a combination thereof may be supported using “incipientwetness”, wherein a solution comprising the activator, the catalystcompound, or a combination thereof is contacted with the support whereinthe amount of the solution is about 95 to about 100 percent of theabsorptive capacity of the support material.

In an embodiment according to the invention, the support material ischemically treated and/or dehydrated prior to combining with thecatalyst compound, activator and/or catalyst system. In an embodimentaccording to the invention, the support material may have various levelsof dehydration, such as may be achieved by drying the support materialat temperatures in the range from about 200° C. to about 1000° C. Thesesupports may also be chemically dehydrated using water reactivecompounds such as silane and organoaluminum compounds.

In an embodiment according to the invention, dehydrated silica may becontacted with an organoaluminum or alumoxane compound. In an embodimentaccording to the invention, wherein an organoaluminum compound is used,the activator is formed in situ in the support material as a result ofthe reaction of, for example, trimethylaluminum and water.

In an embodiment according to the invention, Lewis base-containingsupport substrates will react with a Lewis acidic activator to form asupport bonded Lewis acid compound. The Lewis base hydroxyl groups ofsilica are exemplary of metal/metalloid oxides where this method ofbonding to a support occurs. These embodiments are described in, forexample, U.S. Pat. No. 6,147,173.

Other embodiments of supporting an activator are described in U.S. Pat.No. 5,427,991, where supported non-coordinating anions derived fromtrisperfluorophenyl boron are described; U.S. Pat. No. 5,643,847,discusses the reaction of Group 13 Lewis acid compounds with metaloxides such as silica and illustrates the reaction oftrisperfluorophenyl boron with silanol groups (the hydroxyl groups ofsilicon) resulting in bound anions capable of protonating transitionmetal organometallic catalyst compounds to form catalytically activecations counter-balanced by the bound anions.

In an embodiment according to the invention, the supported activator isformed by preparing, in an agitated, temperature and pressure controlledvessel, a solution of the activator and a suitable solvent, then addingthe support material at temperatures from 0° C. to 100° C., contactingthe support with the activator solution for up to 24 hours, then using acombination of heat and pressure to remove the solvent to produce a freeflowing powder. Temperatures can range from 40 to 120° C. and pressuresfrom 34.5 kPa to 138 kPa (5 psia to 20 psia). An inert gas sweep canalso be used in assist in removing solvent. Alternate orders ofaddition, such as slurrying the support material in an appropriatesolvent then adding the activator, can be used.

In an embodiment according to the invention, the weight percent of theactivator to the support material is in the range from about 10 weightpercent to about 70 weight percent, in the range from about 20 weightpercent to about 60 weight percent in other embodiments, in the rangefrom about 30 weight percent to about 50 weight percent in otherembodiments, and in the range from about 30 weight percent to about 40weight percent in yet other embodiments.

Supported catalysts system useful in embodiments disclosed hereininclude those supported catalyst systems that are formed by contacting asupport material, an activator and a catalyst compound in various waysunder a variety of conditions outside of a catalyst feeder apparatus.

In an embodiment according to the invention, a catalyst compound,activator and support, may be fed into the polymerization reactor as amineral oil slurry or as a slurry in liquid diluent. Solidsconcentrations in the mineral oil or liquid diluent may range from about3 to about 30 weight percent in some embodiments; and from about 10 toabout 25 weight percent in other embodiments.

In an embodiment according to the invention, the catalyst compound(s),activator(s) and/or support(s) used herein may also be spray driedseparately or together prior to being injected into the reactor. Thespray dried catalyst may be used as a powder or solid or may be placedin a diluent and slurried into the reactor. In an embodiment accordingto the invention, a support is combined with one or more activators andis spray dried to form a supported activator. In an embodiment accordingto the invention, fumed silica is combined with methyl alumoxane andthen spray dried to from supported methyl alumoxane, a support may becombined with alumoxane, spray dried and then placed in mineral oil toform a slurry useful according to the instant disclosure. In anembodiment according to the invention, the catalyst compounds describedabove may be combined with one or more support material(s) and/or one ormore activator(s) and spray dried prior to being combined with a slurrydiluent.

In an embodiment according to the invention, the catalyst compoundsand/or the activators are combined with a support material such as aparticulate filler material and then spray dried, which may form a freeflowing powder. Spray drying may be by any means known in the art. In anembodiment according to the invention, the catalyst may be spray driedby placing the catalyst compound and the activator in solution, allowingthe catalyst compound and activator to react, if desired, adding afiller material such as silica and/or fumed silica, then forcing thesolution at high pressures through a nozzle. The solution may be sprayedonto a surface or sprayed such that the droplets dry in midair. Themethod generally employed is to disperse the silica in toluene, stir inthe activator solution, and then stir in the catalyst compound solution.Slurry concentrations may be about 5 to 8 wt %. This formulation may sitas a slurry for as long as 30 minutes with mild stirring or manualshaking to keep it as a suspension before spray-drying. In an embodimentaccording to the invention, the makeup of the dried material is about40-50 wt % activator (e.g., alumoxane), 50-60 SiO₂ and about 2 wt %catalyst compound.

In an embodiment according to the invention, two or more catalystcompounds can be added together in the desired ratio in the last step.In another embodiment, more complex procedures are possible, such asaddition of a first catalyst compound to the activator/filler mixturefor a specified reaction time t, followed by the addition of the secondcatalyst compound solution, mixed for another specified time x, afterwhich the mixture is cosprayed. Lastly, another additive, such as1-hexene in about 10 vol % can be present in the activator/fillermixture prior to the addition of the first catalyst compound.

In an embodiment according to the invention, binders are added to themix. These can be added as a means of improving the particle morphology,i.e. narrowing the particle size distribution, lower porosity of theparticles and allowing for a reduced quantity of alumoxane, which isacting as the “binder”.

In an embodiment according to the invention, spray dried particles arefed into the polymerization reactor as a mineral oil slurry. Solidsconcentrations in oil are about 10 to 30 wt %, or 15 to 25 wt %. In anembodiment according to the invention, the spray dried particles can befrom less than about 10 micrometers in size up to about 100 micrometers,compared to conventional supported catalysts which are about 50micrometers. In an embodiment according to the invention, the supporthas an average particle size of 1 to 50 microns, or 10 to 40 microns.

In an embodiment according to the invention, a catalyst compositionaccording to the instant disclosure is utilized in a catalyst componentslurry and/or in a catalyst component solution. For the purposes of theinstant disclosure, a slurry is defined to be a suspension of a solid,where the solid may or may not be porous, in a liquid. The catalystcomponent slurry and the catalyst component solution are combined toform the catalyst composition which is then introduced into apolymerization reactor. In an embodiment according to the invention, thecatalyst component slurry includes an activator and a support, or asupported activator. In an embodiment according to the invention, theslurry also includes a catalyst compound in addition to the activatorand the support and/or the supported activator. In an embodimentaccording to the invention, the catalyst compound in the slurry issupported. In an embodiment according to the invention, the slurryincludes one or more activator(s) and support(s) and/or supportedactivator(s) and/or one more catalyst compound(s). For example, theslurry may include two or more activators (such as a supported alumoxaneand a modified alumoxane) and a catalyst compound, or the slurry mayinclude a supported activator and more than one catalyst compounds. Inan embodiment according to the invention, the slurry comprises asupported activator and two catalyst compounds.

In an embodiment according to the invention, the slurry comprisessupported activator and two different catalyst compounds, which may beadded to the slurry separately or in combination. In an embodimentaccording to the invention, the slurry, containing a supportedalumoxane, is contacted with a catalyst compound, allowed to react, andthereafter the slurry is contacted with another catalyst compound. Inanother embodiment the slurry containing a supported alumoxane iscontacted with two catalyst compounds at the same time, and allowed toreact. In an embodiment according to the invention, the molar ratio ofmetal in the activator to metal in the catalyst compound in the slurryis 1000:1 to 0.5:1, or 300:1 to 1:1, or 150:1 to 1:1.

Polymerization Processes

In an embodiment according to the invention, a polymerization processincludes contacting monomers (such as ethylene and propylene), andoptionally comonomers, with a catalyst system comprising an activatorand at least one catalyst compound, as described above. In an embodimentaccording to the invention, the catalyst compound and activator may becombined in any order, and may be combined prior to contacting with themonomer. In an embodiment according to the invention, the catalystcompound and/or the activator are combined after contacting with themonomer.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, or C₂ to C₂₀ alpha olefins, or C₂ to C₁₂ alpha olefins,or ethylene, propylene, butene, pentene, hexene, heptene, octene,nonene, decene, undecene, dodecene and isomers thereof. In an embodimentaccording to the invention, the monomer comprises propylene and anoptional comonomer(s) comprising one or more ethylene or C₄ to C₄₀olefins, or C₄ to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₄ to C₄₀olefin monomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups. Inan embodiment according to the invention, the monomer comprises ethyleneor ethylene and a comonomer comprising one or more C₃ to C₄₀ olefins, orC₄ to C₂₀ olefins, or C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomersmay be linear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, or hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, ornorbornene, norbornadiene, and dicyclopentadiene.

In an embodiment according to the invention, one or more dienes arepresent in the polymer produced herein at up to 10 weight %, or at0.00001 to 1.0 weight %, or 0.002 to 0.5 weight %, or 0.003 to 0.2weight %, based upon the total weight of the composition. In anembodiment according to the invention, 500 ppm or less of diene is addedto the polymerization, or 400 ppm or less, or 300 ppm or less. In anembodiment according to the invention, at least 50 ppm of diene is addedto the polymerization, or 100 ppm or more, or 150 ppm or more.

Diolefin monomers useful in this invention include any hydrocarbonstructure, or C₄ to C₃₀, having at least two unsaturated bonds, whereinat least two of the unsaturated bonds are readily incorporated into apolymer by either a stereospecific or a non-stereospecific catalyst(s).In an embodiment according to the invention, the diolefin monomers maybe selected from alpha, omega-diene monomers (i.e. di-vinyl monomers).Preferably, the diolefin monomers are linear di-vinyl monomers, most orthose containing from 4 to 30 carbon atoms. Examples of dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, 1,6-heptadiene,1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene,1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, and lowmolecular weight polybutadienes (Mw less than 1000 g/mol). Cyclic dienesinclude cyclopentadiene, vinylnorbornene, norbornadiene, ethylidenenorbornene, divinylbenzene, dicyclopentadiene or higher ring containingdiolefins with or without substituents at various ring positions.

In an embodiment according to the invention, where butene is thecomonomer, the butene source may be a mixed butene stream comprisingvarious isomers of butene. The 1-butene monomers are expected to bepreferentially consumed by the polymerization process. Use of such mixedbutene streams will provide an economic benefit, as these mixed streamsare often waste streams from refining processes, for example, C₄raffinate streams, and can therefore be substantially less expensivethan pure 1-butene.

Polymerization processes according to the instant disclosure may becarried out in any manner known in the art. Any suspension, homogeneous,bulk, solution, slurry, or gas phase polymerization process known in theart can be used. Such processes can be run in a batch, semi-batch, orcontinuous mode. Homogeneous polymerization processes and slurryprocesses are suitable for use herein; wherein a homogeneouspolymerization process is defined to be a process where at least 90 wt %of the product is soluble in the reaction media. A bulk homogeneousprocess is suitable for use herein, wherein a bulk process is defined tobe a process where monomer concentration in all feeds to the reactor is70 volume % or more. In an embodiment according to the invention, nosolvent or diluent is present or added in the reaction medium, (exceptfor the small amounts used as the carrier for the catalyst system orother additives, or amounts typically found with the monomer; e.g.,propane in propylene). In an embodiment according to the invention, theprocess is a slurry process. As used herein the term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles. At least 95 wt % of polymer products derived fromthe supported catalyst is in granular form as solid particles (notdissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄₋₁₀ alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene,and xylene. Suitable solvents also include liquid olefins which may actas monomers or comonomers including ethylene, propylene, 1-butene,1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene,1-decene, and mixtures thereof. In an embodiment according to theinvention, aliphatic hydrocarbon solvents are used as the solvent, suchas isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In an embodiment according tothe invention, the solvent is not aromatic, or aromatics are present inthe solvent at less than 1 wt %, or less than 0.5 wt %, or less than 0.0wt % based upon the weight of the solvents.

In an embodiment according to the invention, the feed concentration ofthe monomers and comonomers for the polymerization is 60 vol % solventor less, or 40 vol % or less, or 20 vol % or less, based on the totalvolume of the feedstream. The polymerization may also be run in a bulkprocess.

Polymerizations can be run at any temperature and/or pressure suitableto obtain the desired ethylene polymers. Suitable temperatures and/orpressures include a temperature in the range of from about 0° C. toabout 300° C., or about 20° C. to about 200° C., or about 35° C. toabout 150° C., or about 50° C. to about 150° C., or from about 40° C. toabout 120° C., or from about 45° C. to about 80° C.; and at a pressurein the range of from about 0.35 MPa to about 10 MPa, or from about 0.45MPa to about 6 MPa, or from about 0.5 MPa to about 4 MPa.

In an embodiment according to the invention, the run time of thereaction is from about 0.1 minutes to about 24 hours, or up to 16 hours,or in the range of from about 5 to 250 minutes, or from about 10 to 120minutes.

In an embodiment according to the invention, hydrogen is present in thepolymerization reactor at a partial pressure of 0.007 kPa to 345 kPa(0.001 to 50 psig), or from 0.07 kPa to 172 kPa (0.01 to 25 psig), or0.7 kPa to 70 kPa (0.1 to 10 psig).

In an embodiment according to the invention, the activity of thecatalyst is at least 50 g/mmol/hour, or 500 or more g/mmol/hour, or 5000or more g/mmol/hr, or 50,000 or more g/mmol/hr. In an alternateembodiment, the conversion of olefin monomer is at least 10%, based uponpolymer yield and the weight of the monomer entering the reaction zone,or 20% or more, or 30% or more, or 50% or more, or 80% or more.

In an embodiment according to the invention, the polymerizationconditions include one or more of the following: 1) temperatures of 0 to300° C. (or 25 to 150° C., or 40 to 120° C., or 45 to 80° C.); 2) apressure of atmospheric pressure to 10 MPa (or 0.35 to 10 MPa, or from0.45 to 6 MPa, or from 0.5 to 4 MPa); 3) the presence of an aliphatichydrocarbon solvent (such as isobutane, butane, pentane, isopentane,hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof;cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof; or wherearomatics are or present in the solvent at less than 1 wt %, or lessthan 0.5 wt %, or at 0 wt % based upon the weight of the solvents); 4)wherein the catalyst system used in the polymerization comprises lessthan 0.5 mol %, or 0 mol % alumoxane, or the alumoxane is present at amolar ratio of aluminum to transition metal less than 500:1, or lessthan 300:1, or less than 100:1, or less than 1:1; 5) the polymerizationor occurs in one reaction zone; 6) the productivity of the catalystcompound is at least 80,000 g/mmol/hr (or at least 150,000 g/mmol/hr, orat least 200,000 g/mmol/hr, or at least 250,000 g/mmol/hr, or at least300,000 g/mmol/hr); 7) scavengers (such as trialkyl aluminum compounds)are absent (e.g., present at zero mol %) or the scavenger is present ata molar ratio of scavenger to transition metal of less than 100:1, orless than 50:1, or less than 15:1, or less than 10:1; and/or 8)optionally hydrogen is present in the polymerization reactor at apartial pressure of 0.007 to 345 kPa (0.001 to 50 psig) (or from 0.07 to172 kPa (0.01 to 25 psig), or 0.7 to 70 kPa (0.1 to 10 psig)).

In an embodiment according to the invention, the catalyst system used inthe polymerization comprises no more than one catalyst compound. A“reaction zone” also referred to as a “polymerization zone” is a vesselwhere polymerization takes place, for example a batch reactor. Whenmultiple reactors are used in either series or parallel configuration,each reactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In an embodiment according to the invention, thepolymerization occurs in one reaction zone.

Polyolefin Products

The instant disclosure also relates to compositions of matter producedby the methods described herein.

In an embodiment according to the invention, the process describedherein produces propylene homopolymers or propylene copolymers, such aspropylene-ethylene and/or propylene-α-olefin (or C₃ to C₂₀) copolymers(such as propylene-hexene copolymers or propylene-octene copolymers)having an Mw/Mn of greater than 1 to 4 (or greater than 1 to 3).

Likewise, the process of this invention produces olefin polymers, orpolyethylene and polypropylene homopolymers and copolymers. In anembodiment according to the invention, the polymers produced herein arehomopolymers of ethylene or propylene, are copolymers of ethylene orhaving from 0 to 25 mole % (or from 0.5 to 20 mole %, or from 1 to 15mole %, or from 3 to 10 mole %) of one or more C₃ to C₂₀ olefincomonomer (or C₃ to C₁₂ alpha-olefin, or propylene, butene, hexene,octene, decene, dodecene, or propylene, butene, hexene, octene), or arecopolymers of propylene or having from 0 to 25 mole % (or from 0.5 to 20mole %, or from 1 to 15 mole %, or from 3 to 10 mole %) of one or moreof C₂ or C₄ to C₂₀ olefin comonomer (or ethylene or C₄ to C₁₂alpha-olefin, or ethylene, butene, hexene, octene, decene, dodecene, orethylene, butene, hexene, octene).

In an embodiment according to the invention, the monomer is ethylene andthe comonomer is hexene, or from 1 to 15 mole % hexene, or 1 to 10 mole% hexene.

In an embodiment according to the invention, the polymers producedherein have an Mw of 5,000 to 1,000,000 g/mol (e.g., 25,000 to 750,000g/mol, or 50,000 to 500,000 g/mol), and/or an Mw/Mn of greater than 1 to40, or 1.2 to 20, or 1.3 to 10, or 1.4 to 5, or 1.5 to 4, or 1.5 to 3.

In an embodiment according to the invention, the polymer produced hereinhas a unimodal or multimodal molecular weight distribution as determinedby Gel Permeation Chromatography (GPC). By “unimodal” is meant that theGPC trace has one peak or inflection point. By “multimodal” is meantthat the GPC trace has at least two peaks or inflection points. Aninflection point is that point where the second derivative of the curvechanges in sign (e.g., from negative to positive or vice versa).

Unless otherwise indicated Mw, Mn, MWD are determined by GPC asdescribed in US 2006/0173123 page 24-25, paragraphs [0334] to [0341],and/or by ¹H NMR as described herein.

In an embodiment according to the invention, the polymers may be linearin character, which may be determined by elution fractionation, whereinnon-linear polymers have a CDBI of less than 45%, whereas linearpolyethylene types refer to polyethylene having a CDBI of greater than50%, the CDBI being determined as described in WO93/03093 (U.S. Pat. No.5,206,075). In an embodiment according to the invention, the polymerproduced herein has a composition distribution breadth index (CDBI) of50% or more, or 60% or more, or 70% or more. CDBI is a measure of thecomposition distribution of monomer within the polymer chains and ismeasured by the procedure described in PCT publication WO 93/03093,published Feb. 18, 1993, specifically columns 7 and 8 as well as in Wildet al, J. Poly. Sci., Poly. Phys. Ed., Vol. 20, p. 441 (1982) and U.S.Pat. No. 5,008,204, including that fractions having a weight averagemolecular weight (Mw) below 15,000 are ignored when determining CDBI.

Polymers with an Mw/Mn of 4.5 or less may include a significant level oflong chain branching. The long chain branching is understood to be theresult of the incorporation of terminally unsaturated polymer chains(formed by the specific termination reaction mechanism encountered withsingle site catalysts) into other polymer chains in a manner analogousto monomer incorporation. The branches are hence believed to be linearin structure and may be present at a level where no peaks can bespecifically attributed to such long chain branches in the ¹³C NMRspectrum. In an embodiment according to the invention, the polymersproduced according to the instant disclosure comprise a significantamount of long chain branching, defined as having a ratio of long chainbranching of at least 7 carbons per 1000 carbon atoms as determinedaccording to the ¹³C NMR spectrum of greater than 0.5. In an embodimentaccording to the invention, the ratio of long chain branching withbranches having at least 7 carbons, per 1000 carbon atoms as determinedaccording to the ¹³C NMR spectrum is greater than 1, or greater than1.5, or greater than 2.

In an embodiment according to the invention, the polymers producedaccording to the instant disclosure include a significant amount ofvinyl termination, defined as a ratio of vinyl groups per molecule ofgreater than or equal to 0.2. In an embodiment according to theinvention, the polymers according to the instant disclosure comprise aratio of vinyl groups per molecule of greater than or equal to 0.5, or0.7, or 0.8, or 0.9, or 0.95, when determined according to thedescription provided in the J. American Chemical Soc., 114, 1992, pp.1025-1032, or an equivalent thereof.

In an embodiment according to the invention, propylene polymer producedusing the instant catalyst comprise at least 50% vinyl or unsaturatedchain ends. In an embodiment of the invention, at least 90%, or at least95%, or at least 99% vinylidene chain ends.

In an embodiment according to the invention, the polyolefins producedusing the instant catalyst may be isotactic, highly isotactic,syndiotactic, or highly syndiotactic propylene polymer. As used herein,“isotactic” is defined as having at least 10% isotactic pentads,preferably having at least 40% isotactic pentads of methyl groupsderived from propylene according to analysis by ¹³C-NMR. As used herein,“highly isotactic” is defined as having at least 60% isotactic pentadsaccording to analysis by ¹³C-NMR. In a desirable embodiment, the vinylterminated polyolefin (preferably polypropylene) has at least 85%isotacticity. As used herein, “syndiotactic” is defined as having atleast 10% syndiotactic pentads, preferably at least 40%, according toanalysis by ¹³C-NMR. As used herein, “highly syndiotactic” is defined ashaving at least 60% syndiotactic pentads according to analysis by¹³C-NMR. In an embodiment according to the invention, the vinylterminated polyolefin (preferably polypropylene) has at least 85%syndiotacticity.

This invention relates to ethylene polymers having both vinyltermination and long chain branching, which in an embodiment accordingto the invention, are produced by the processes and using the catalystdisclosed herein. In an embodiment according to the invention, theprocess described herein produces ethylene homopolymers or ethylenecopolymers, such as ethylene-alpha-olefin, or C₃ to C₂₀ copolymers suchas ethylene-propylene copolymers, ethylene-hexene copolymers orethylene-octene copolymers having:

a) at least 50% allyl chain ends, or least 60%, 70%, 80%, 90%, 95%, 98%,or 99%; and/or

b) an Mn of at least 200 g/mol, measured by ¹H NMR, or 250 g/mol to100,000 g/mol, e.g., or 200 g/mol to 75,000 g/mol, e.g., or 200 g/mol to60,000 g/mol, or 300 g/mol to 60,000 g/mol, or 750 g/mol to 30,000g/mol); and/or

c) at least 0.5 branches having 7 or more carbon atoms per 1000 carbonatoms, or 1.0 or more, or 1.25 or more, or 1.5 or more, or 1.75 or more,or 2.0 or more, or from 0.5 to 5.0, or from 1.0 to 4.0, or from 1.5 to3.0; and/or

d) a Tm of 100° C. or more, or 110° C. or more, or 120° C. or more;and/or

e) a ratio of methyl chain ends, also referred to herein as saturatedchain ends, to allyl chain ends of 1:1 to 5:1, or 1:1 to 4:1, or 1:1 to3:1; and/or

f) at least 50 wt % of the polymer, which may be an ethylene homopolymeror copolymer, has one vinyl per molecule or per chain as determined by¹H NMR, or at least 60 wt %, or at least 70 wt %, or at least 80 wt %,or at least 90 wt %, or at least 95 wt %; and/or essentially no diene ispresent, or the polymer comprises less than or equal to about 0.01 wt %diene; and/or

g) the polymer comprises at least 50 mol % ethylene, or at least 60 mol%, or at least 70 mol %, or at least 75 mol %, or at least 80 mol %, orat least 85 mol %, or at least 90 mol %, or at least 95 mol %, oressentially 100 mol % ethylene; and/or

h) an Mw/Mn of greater than 1 to 4, or greater than 1 to 3.

In an embodiment according to the invention, polymer produced herein hasless than 1400 ppm aluminum, or less than 1200 ppm, or less than 1000ppm, or less than 500 ppm, or less than 100 ppm as determined by ICPES(Inductively Coupled Plasma Emission Spectrometry), which is describedin J. W. Olesik, “Inductively Coupled Plasma-Optical EmissionSpectroscopy,” in the Encyclopedia of Materials Characterization, C. R.Brundle, C. A. Evans, Jr. and S. Wilson, eds., Butterworth-Heinemann,Boston, Mass., 1992, pp. 633-644, which is used herein for purposes ofdetermining the amount of an element in a material; and/or in anembodiment according to the invention, the polymer has less than 1400ppm of the Group 3, 4, 5, or 6 transition metal, or of the Group 4transition metal, or of Ti, Zr, and/or Hf, or less than 1200 ppm, orless than 1000 ppm, or less than 500 ppm, or less than 100 ppm, asdetermined by ICPES as discussed above.

In an embodiment according to the invention, an ethylene polymeraccording to the instant disclosure has less than 1400 ppm hafnium, orless than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or lessthan 100 ppm as determined by ICPES.

In an embodiment according to the invention, an ethylene polymeraccording to the instant disclosure has less than 1400 ppm zirconium, orless than 1200 ppm, or less than 1000 ppm, or less than 500 ppm, or lessthan 100 ppm as determined by ICPES.

In an embodiment according to the invention, the polymer producedherein, which may be an ethylene polymer, has a density of greater than0.95 g/cc, or greater than 0.955 g/cc, or greater than 0.96 g/cc.

In an embodiment according to the invention, the ethylene polymerproduced herein has a branching index (g′vis) of 0.9 or less, or 0.85 orless, or 0.80 or less, where g′vis is determined as described below.

For purposes herein, Mw, Mz number of carbon atoms, g value and g′_(vis)are determined by using a High Temperature Size Exclusion Chromatograph(either from Waters Corporation or Polymer Laboratories), equipped withthree in-line detectors, a differential refractive index detector (DRI),a light scattering (LS) detector, and a viscometer. Experimentaldetails, including detector calibration, are described in: T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, 6812-6820, (2001) and references therein. Three PolymerLaboratories PLgel 10 mm Mixed-B LS columns are used. The nominal flowrate is 0.5 cm³/min, and the nominal injection volume is 300 μL. Thevarious transfer lines, columns and differential refractometer (the DRIdetector) are contained in an oven maintained at 145° C. Solvent for theexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SizeExclusion Chromatograph. Polymer solutions are prepared by placing drypolymer in a glass container, adding the desired amount of TCB, thenheating the mixture at 160° C. with continuous agitation for about 2hours. All quantities are measured gravimetrically. The TCB densitiesused to express the polymer concentration in mass/volume units are 1.463g/ml at room temperature and 1.324 g/ml at 14 5° C. The injectionconcentration is from 0.75 to 2.0 mg/ml, with lower concentrations beingused for higher molecular weight samples. Prior to running each samplethe DRI detector and the injector are purged. Flow rate in the apparatusis then increased to 0.5 ml/minute, and the DRI is allowed to stabilizefor 8 to 9 hours before injecting the first sample. The LS laser isturned on 1 to 1.5 hours before running the samples. The concentration,c, at each point in the chromatogram is calculated from thebaseline-subtracted DRI signal, I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 145° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymers,0.098 for butene polymers and 0.1 otherwise. Units on parametersthroughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The LS detector is a Wyatt Technology High Temperature mini-DAWN. Themolecular weight, M, at each point in the chromatogram is determined byanalyzing the LS output using the Zimm model for static light scattering(M. B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press,1971):

$\frac{K_{o}c}{\Delta\;{R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{2}c}}$Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient [for purposes of thisinvention, A₂=0.0006 for propylene polymers, 0.0015 for butene polymersand 0.001 otherwise], (dn/dc)=0.104 for propylene polymers, 0.098 forbutene polymers and 0.1 otherwise, P(θ) is the form factor for amonodisperse random coil, and K_(o) is the optical constant for thesystem:

$K_{o} = \frac{4\pi^{2}{n^{2}( {{\mathbb{d}n}/{\mathbb{d}c}} )}^{2}}{\lambda^{4}N_{A}}$where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=690 nm.

A high temperature Viscotek Corporation viscometer, which has fourcapillaries arranged in a Wheatstone bridge configuration with twopressure transducers, is used to determine specific viscosity. Onetransducer measures the total pressure drop across the detector, and theother, positioned between the two sides of the bridge, measures adifferential pressure. The specific viscosity, η_(s), for the solutionflowing through the viscometer is calculated from their outputs. Theintrinsic viscosity, [η], at each point in the chromatogram iscalculated from the following equation:η_(s) =c[η]+0.3(c[η])²where c is concentration and was determined from the DRI output.

The branching index (g′_(vis)) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$where the summations are over the chromatographic slices, i, between theintegration limits. The branching index g′_(vis) is defined as:

${g^{\prime}{vis}} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$where, for purpose of this invention and claims thereto, α=0.695 andk=0.000579 for linear ethylene polymers, α=0.705 k=0.000262 for linearpropylene polymers, and α=0.695 and k=0.000181 for linear butenepolymers. M_(v) is the viscosity-average molecular weight based onmolecular weights determined by LS analysis.

Also called a “g value”, “g” is defined to be Rg² _(pm)/Rg² _(ls), whereRg_(pm) is the radius of gyration for the polymacromer, Rg² _(ls) is theradius of gyration for the linear standard, and Rg_(ls)=KsM^(0.58) whereK_(s) is the power law coefficient (0.023 for linear polyethylene,0.0171 for linear polypropylene, and 0.0145 for linear polybutene), andM is the molecular weight as described above, Rg_(pm)=K_(T)M^(αs), α_(s)is the size coefficient for the polymacromer, K_(T) is the power lawcoefficient for the polymacromer. See Macromolecules, 2001, 34,6812-6820, for guidance on selecting a linear standards having themolecular weight and comonomer content, and determining K coefficientsand α exponents.

In an embodiment of the invention, the instant catalyst is used toproduce vinyl terminated polymers having unsaturated chain end orterminus. The unsaturated chain end of the vinyl terminated macromonomercomprises an “allyl chain end”, a vinylidene chain end, or a “3-alkyl”chain end.

An allyl chain end is represented by CH₂CH—CH₂—, as shown in theformula:

where M represents the polymer chain. “Allylic vinyl group,” “allylchain end,” “vinyl chain end,” “vinyl termination,” “allylic vinylgroup,” and “vinyl terminated” are used interchangeably in the followingdescription. The number of allyl chain ends, vinylidene chain ends,vinylene chain ends, and other unsaturated chain ends is determinedusing ¹H NMR at 120° C. using deuterated tetrachloroethane as thesolvent on an at least 250 MHz NMR spectrometer, and in selected cases,confirmed by ¹³C NMR. Resconi has reported proton and carbon assignments(neat perdeuterated tetrachloroethane used for proton spectra, while a50:50 mixture of normal and perdeuterated tetrachloroethane was used forcarbon spectra; all spectra were recorded at 100° C. on a BRUKERspectrometer operating at 500 MHz for proton and 125 MHz for carbon) forvinyl terminated oligomers in J. American Chemical Soc., 114, 1992, pp.1025-1032 that are useful herein. Allyl chain ends are reported as amolar percentage of the total number of moles of unsaturated groups(that is, the sum of allyl chain ends, vinylidene chain ends, vinylenechain ends, and the like).

A vinylidene chain end is represented by the formula:

where R can be H, alkyl, aryl aralkyl, or alkaryl.

A 3-alkyl chain end (where the alkyl is a C₁ to C₃₈ alkyl), alsoreferred to as a “3-alkyl vinyl end group” or a “3-alkyl vinyltermination”, is represented by the formula:

where “••••” represents the polyolefin chain and R^(b) is a C₁ to C₃₈alkyl group, or a C₁ to C₂₀ alkyl group, such as methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, andthe like. The amount of 3-alkyl chain ends is determined using ¹³C NMRas set out below.

¹³C NMR data may be collected at 120° C. at a frequency of at least 100MHz, using a BRUKER 400 MHz NMR spectrometer. A 90 degree pulse, anacquisition time adjusted to give a digital resolution between 0.1 and0.12 Hz, at least a 10 second pulse acquisition delay time withcontinuous broadband proton decoupling using swept square wavemodulation without gating is employed during the entire acquisitionperiod. The spectra is acquired with time averaging to provide a signalto noise level adequate to measure the signals of interest. Samples aredissolved in tetrachloroethane-d₂ at concentrations between 10 wt % to15 wt % prior to being inserted into the spectrometer magnet. Prior todata analysis spectra are referenced by setting the chemical shift ofthe TCE solvent signal to 74.39 ppm. Chain ends for quantization wereidentified using the signals shown in the table below. Unless otherwiseindicated, n-butyl and n-propyl may not be reported if their abundanceis less than 5% relative to the chain ends detected.

In the alternative, ¹³C NMR data may be collected at 120° C. in a 10 mmprobe using a Varian spectrometer with a ¹H frequency of at least 400MHz. A 90 degree pulse, an acquisition time adjusted to give a digitalresolution between 0.1 and 0.12 Hz, at least a 10 second pulseacquisition delay time with continuous broadband proton decoupling usingswept square wave modulation without gating was employed during theentire acquisition period. The spectra were acquired using timeaveraging to provide a signal to noise level adequate to measure thesignals of interest. Samples were dissolved in tetrachloroethane-d₂ atconcentrations between 10 to 15 wt % prior to being inserted into thespectrometer magnet. Prior to data analysis spectra were referenced bysetting the chemical shift of the (—CH₂—)_(n) signal where n>6 to 29.9ppm. Chain ends for quantization were identified using the signals shownin the table below. N-butyl and n-propyl were not reported due to theirlow abundance (less than 5%) relative to the chain ends shown in thetable below.

Chain End ¹³CNMR Chemical Shift P~i-Bu 23-5 to 25.5 and 25.8 to 26.3 ppmE~i-Bu 39.5 to 40.2 ppm P~Vinyl 41.5 to 43 ppm E~Vinyl 33.9 to 34.4 ppm

Samples are dissolved in d₂-1,1,2,2-tetrachloroethane, and spectrarecorded at 125° C. using a 100 MHz (or higher) NMR spectrometer.Polymer resonance peaks are referenced to mmmm=21.8 ppm. Calculationsinvolved in the characterization of polymers by NMR are described by F.A. Bovey in Polymer Conformation and Configuration (Academic Press, NewYork 1969) and J. Randall in Polymer Sequence Determination, ¹³C-NMRMethod (Academic Press, New York, 1977).

The “allyl chain end to vinylidene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylidene chain ends.

The “allyl chain end to vinylene chain end ratio” is defined to be theratio of the percentage of allyl chain ends to the percentage ofvinylene chain ends.

Vinyl terminated polymers typically also have a saturated chain end,also referred to as a methyl end. In polymerizations comprising C₄ orgreater monomers (or “higher olefin” monomers), the saturated chain endmay be a C₄ or greater (or “higher olefin”) chain end, as shown in theformula below:

where M represents the polymer chain and n is an integer selected from 4to 40. This is especially true when there is substantially no ethyleneor propylene in the polymerization. In an ethylene/(C₄ or greatermonomer) copolymerization, the polymer chain may initiate growth in anethylene monomer, thereby generating a saturated chain end which is anethyl chain end. In polymerizations where propylene is present, thepolymer chain may initiate growth in a propylene monomer, therebygenerating an isobutyl chain end. An “isobutyl chain end” is defined tobe an end or terminus of a polymer, represented as shown in the formulabelow:

where M represents the polymer chain. Isobutyl chain ends are determinedaccording to the procedure set out in WO 2009/155471. The “isobutylchain end to allylic vinyl group ratio” is defined to be the ratio ofthe percentage of isobutyl chain ends to the percentage of allyl chainends.

In an embodiment of the invention, the propylene polymer produced usingthe instant catalyst comprises at least 50% vinyl or unsaturated chainends. In an embodiment of the invention, at least 90%, or at least 95%,or at least 99% vinylidene chain ends.

Mn (¹H NMR) may be determined according to the following NMR method. ¹HNMR data is collected at either room temperature or 120° C. (forpurposes of the claims, 120° C. shall be used) in a 5 mm probe using aVarian spectrometer with a ¹H frequency of 250 MHz, 400 MHz, or 500 MHz(for the purpose of the claims, a proton frequency of 400 MHz is used).Data are recorded using a maximum pulse width of 45° C., 8 secondsbetween pulses and signal averaging 120 transients. Spectral signals areintegrated and the number of unsaturation types per 1000 carbons arecalculated by multiplying the different groups by 1000 and dividing theresult by the total number of carbons. Mn is calculated by dividing thetotal number of unsaturated species into 14,000, and has units of g/mol.The chemical shift regions for the olefin types are defined to bebetween the following spectral regions.

Number of hydrogens Unsaturation Type Region (ppm) per structure AllylicVinyl 4.95-5.10 2 Vinylidene 4.70-4.84 2 Disubstituted Vinylene5.31-5.55 2 Trisubstituted Vinylene 5.11-5.30 1Differential Scanning Calorimetry (DSC)

Crystallization temperature (T_(c)), melting temperature (or meltingpoint, T_(m)), glass transition temperature (T_(g)) and heat of fusion(Hf) are measured using Differential Scanning calorimetry (DSC) on acommercially available instrument (e.g., TA Instruments 2920 DSC).Typically, 6 to 10 mg of molded polymer or plasticized polymer aresealed in an aluminum pan and loaded into the instrument at roomtemperature. Data are acquired by heating the sample to at least 30° C.above its melting temperature, typically 220° C. for polypropylene, at aheating rate of 10° C./min. The sample is held for at least 5 minutes atthis temperature to destroy its thermal history. Then the sample iscooled from the melt to at least 50° C. below the crystallizationtemperature, typically −100° C. for polypropylene, at a cooling rate of20° C./min. The sample is held at this temperature for at least 5minutes, and finally heated at 10° C./min to acquire additional meltingdata (second heat). The endothermic melting transition (first and secondheat) and exothermic crystallization transition are analyzed accordingto standard procedures. The melting temperatures (Tm) reported are thepeak melting temperatures from the second heat unless otherwisespecified. For polymers displaying multiple peaks, the meltingtemperature is defined to be the peak melting temperature from themelting trace associated with the largest endothermic calorimetricresponse (as opposed to the peak occurring at the highest temperature).Likewise, the crystallization temperature is defined to be the peakcrystallization temperature from the crystallization trace associatedwith the largest exothermic calorimetric response (as opposed to thepeak occurring at the highest temperature).

Areas under the DSC curve are used to determine the heat of transition(heat of fusion, H_(f), upon melting or heat of crystallization, H_(c),upon crystallization), which can be used to calculate the degree ofcrystallinity (also called the percent crystallinity). The percentcrystallinity (X %) is calculated using the formula: [area under thecurve (in J/g)/H^(o) (in J/g)]*100, where H^(o) is the ideal heat offusion for a perfect crystal of the homopolymer of the major monomercomponent. These values for H^(o) are to be obtained from the PolymerHandbook, Fourth Edition, published by John Wiley and Sons, New York1999, except that a value of 290 J/g is used for H^(o) (polyethylene), avalue of 140 J/g is used for H^(o) (polybutene), and a value of 207 J/gis used for H^(o) (polypropylene).

Heat of melting (Hm) is determined using the DSC procedure above exceptthat the sample is cooled to −100° C., held for 5 minutes then heated at10° C./min to 200° C. Hm is measured on the first melt, no the secondmelt. The Hm sample must have been aged at least 48 hours at roomtemperature and should not be heated to destroy thermal history.

Ethylene Content

Ethylene content in ethylene copolymers is determined by ASTM D 5017-96,or an equivalent thereof, except that the minimum signal-to-noise shouldbe 10,000:1. Propylene content in propylene copolymers is determined byfollowing the approach of Method 1 in Di Martino and Kelchermans, J.Appl. Polym. Sci. 56, 1781 (1995), and using peak assignments fromZhang, Polymer 45, 2651 (2004) for higher olefin comonomers.

Mn, Mw, and Mz may also be measured by using a Gel PermeationChromatography (GPC) method using a High Temperature Size ExclusionChromatograph (SEC, either from Waters Corporation or PolymerLaboratories), equipped with a differential refractive index detector(DRI). Experimental details, are described in: T. Sun, P. Brant, R. R.Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, pp.6812-6820, (2001) and references therein. Three Polymer LaboratoriesPLgel 10 mm Mixed-B columns are used. The nominal flow rate is 0.5cm³/min and the nominal injection volume is 300 μl. The various transferlines, columns and differential refractometer (the DRI detector) arecontained in an oven maintained at 135° C. Solvent for the SECexperiment is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. TheTCB is then degassed with an online degasser before entering the SEC.Polymer solutions are prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities aremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/mL at room temperatureand 1.324 g/mL at 135° C. The injection concentration is from 1.0 to 2.0mg/mL, with lower concentrations being used for higher molecular weightsamples. Prior to running each sample the DRI detector and the injectorare purged. Flow rate in the apparatus is then increased to 0.5mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours beforeinjecting the first sample. The concentration, c, at each point in thechromatogram is calculated from the baseline-subtracted DRI signal,I_(DRI), using the following equation:c=K _(DRI) I _(DRI)/(dn/dc)where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. The refractiveindex, n=1.500 for TCB at 135° C. and λ=690 nm. For purposes of thisinvention and the claims thereto (dn/dc)=0.104 for propylene polymersand ethylene polymers, and 0.1 otherwise. Units of parameters usedthroughout this description of the SEC method are: concentration isexpressed in g/cm³, molecular weight is expressed in g/mol, andintrinsic viscosity is expressed in dL/g.Blends

In an embodiment according to the invention, the polymer (or thepolyethylene or polypropylene) produced herein is combined with one ormore additional polymers prior to being formed into a film, molded partor other article. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene, and/orbutene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE,HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, cross linkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene.

In an embodiment according to the invention, the polymer (or thepolyethylene or polypropylene) is present in the above blends, at from10 to 99 wt %, based upon the weight of the polymers in the blend, or 20to 95 wt %, or at least 30 to 90 wt %, or at least 40 to 90 wt %, or atleast 50 to 90 wt %, or at least 60 to 90 wt %, or at least 70 to 90 wt%.

The blends described above may be produced by mixing the polymers of theinvention with one or more polymers (as described above), by connectingreactors together in series to make reactor blends or by using more thanone catalyst in the same reactor to produce multiple species of polymer.The polymers can be mixed together prior to being put into the extruderor may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such as IRGANOX1010 or IRGANOX 1076 available from Ciba-Geigy); phosphites (e.g.,IRGAFOS 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

In an embodiment according to the invention, any of the foregoingpolymers, such as the foregoing polypropylenes or blends thereof, may beused in a variety of end-use applications. Applications include, forexample, mono- or multi-layer blown, extruded, and/or shrink films.These films may be formed by any number of well-known extrusion orcoextrusion techniques, such as a blown bubble film processingtechnique, wherein the composition can be extruded in a molten statethrough an annular die and then expanded to form a uniaxial or biaxialorientation melt prior to being cooled to form a tubular, blown film,which can then be axially slit and unfolded to form a flat film. Filmsmay be subsequently unoriented, uniaxially oriented, or biaxiallyoriented to the same or different extents. One or more of the layers ofthe film may be oriented in the transverse and/or longitudinaldirections to the same or different extents. The uniaxial orientationcan be accomplished using typical cold drawing or hot drawing methods.Biaxial orientation can be accomplished using tenter frame equipment ora double bubble processes and may occur before or after the individuallayers are brought together. For example, a polyethylene layer can beextrusion coated or laminated onto an oriented polypropylene layer orthe polyethylene and polypropylene can be coextruded together into afilm then oriented. Likewise, oriented polypropylene could be laminatedto oriented polyethylene or oriented polyethylene could be coated ontopolypropylene then optionally the combination could be oriented evenfurther. Typically the films are oriented in the machine direction (MD)at a ratio of up to 15, or between 5 and 7, and in the transversedirection (TD) at a ratio of up to 15, or 7 to 9. However, in anembodiment according to the invention, the film is oriented to the sameextent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick. Thethickness of the sealing layer is typically 0.2 to 50 μm. There may be asealing layer on both the inner and outer surfaces of the film or thesealing layer may be present on only the inner or the outer surface.

In an embodiment according to the invention, one or more layers may bemodified by corona treatment, electron beam irradiation, gammairradiation, flame treatment, or microwave. In an embodiment accordingto the invention, one or both of the surface layers is modified bycorona treatment.

Molded Products

The compositions described herein (or polypropylene compositions) mayalso be used to prepare molded products in any molding process,including but not limited to, injection molding, gas-assisted injectionmolding, extrusion blow molding, injection blow molding, injectionstretch blow molding, compression molding, rotational molding, foammolding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

Further, the compositions described herein (or polypropylenecompositions) may be shaped into desirable end use articles by anysuitable means known in the art. Thermoforming, vacuum forming, blowmolding, rotational molding, slush molding, transfer molding, wet lay-upor contact molding, cast molding, cold forming matched-die molding,injection molding, spray techniques, profile co-extrusion, orcombinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. Typically, an extrudate film of the composition ofthis invention (and any other layers or materials) is placed on ashuttle rack to hold it during heating. The shuttle rack indexes intothe oven which pre-heats the film before forming. Once the film isheated, the shuttle rack indexes back to the forming tool. The film isthen vacuumed onto the forming tool to hold it in place and the formingtool is closed. The tool stays closed to cool the film and the tool isthen opened. The shaped laminate is then removed from the tool. Thethermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution.

Blow molding is another suitable forming means for use with thecompositions of this invention, which includes injection blow molding,multi-layer blow molding, extrusion blow molding, and stretch blowmolding, and is especially suitable for substantially closed or hollowobjects, such as, for example, gas tanks and other fluid containers.Blow molding is described in more detail in, for example, CONCISEENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I.Kroschwitz, ed., John Wiley & Sons 1990).

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheets may be made either byextruding a substantially flat profile from a die, onto a chill roll, orby calendaring. Sheets are generally considered to have a thickness offrom 254 μm to 2540 μm (10 mils to 100 mils), although any given sheetmay be substantially thicker.

Non-Wovens and Fibers

The polyolefin compositions described above may also be used to preparenonwoven fabrics and fibers of this invention in any nonwoven fabric andfiber making process, including but not limited to, melt blowing,spunbonding, film aperturing, and staple fiber carding. A continuousfilament process may also be used, or a spunbonding process may be used.The spunbonding process is well known in the art. Generally it involvesthe extrusion of fibers through a spinneret. These fibers are then drawnusing high velocity air and laid on an endless belt. A calender roll isgenerally then used to heat the web and bond the fibers to one anotheralthough other techniques may be used such as sonic bonding and adhesivebonding.

Embodiments

Accordingly, the instant disclosure relates to the followingembodiments:

-   -   A. A process comprising: contacting one or more olefins with a        catalyst system at a temperature, a pressure, and for a period        of time sufficient to produce a polyolefin; the catalyst system        comprising an activator and a catalyst compound disposed on a        support.    -   B. The process of embodiment A, wherein the catalyst compound        comprises a Salan catalyst compound.    -   C. The process of embodiment A or embodiment B wherein the        catalyst compound comprises a compound according to Formula I,        Formula I being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², N³ and N⁴ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,            R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            two or more of R¹ to R²⁸ may independently join together to            form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a            combination thereof, or a combination thereof; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl.

    -   D. The process of embodiment C, wherein one or more of R¹, R²,        R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,        R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸        of Formula I is a methyl radical, a fluoride, or a combination        thereof.

    -   E. The process of embodiment C or embodiment D, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   F. The process of embodiment C or embodiment D, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are            hydrogen; and        -   Y is —CH₂CH₂—.

    -   G. The process of embodiment C or embodiment D, wherein:

    -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R⁴ and R¹⁷ are fluoro groups;        -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are            hydrogen; and        -   Y is —CH₂CH₂—.

    -   H. The process of embodiment C or embodiment D, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R⁸, R¹¹, R²¹ and R²⁴ are tert-butyl radicals;        -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,            R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   I. The process of embodiment C or embodiment D, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;        -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,            R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   J. The process of any one of embodiments A to I wherein the        catalyst compound comprises a compound according to Formula II,        Formula II being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², and N³ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²¹            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;            subject to the proviso that R¹⁹ is not a carbazole or a            substituted carbazole radical, and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

    -   K. The process of embodiment J, wherein one or more of R¹, R²,        R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶,        R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ according to Formula II, is a methyl        radical, a bromide, an adamantyl radical, or a combination        thereof.

    -   L. The process of embodiment J or embodiment K, wherein in the        catalyst compound according to Formula II:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;        -   R¹⁷ and R¹⁹ are bromine; and        -   Y is —CH₂CH₂—.

    -   M. The process of embodiment J or embodiment K, wherein in the        catalyst compound according to Formula II:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R¹⁴ and R¹⁷ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰, and R²¹ are hydrogen;        -   R¹⁹ is a 1-adamantyl radical; and        -   Y is —CH₂CH₂—.

    -   N. The process of embodiment J or embodiment K, wherein in the        catalyst compound according to Formula II:        -   M is Hf;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ and R¹⁷ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;        -   R¹⁹ is a 1-adamantyl radical; and        -   Y is —CH₂CH₂—.

    -   O. The process of any one of embodiments A to N wherein the        catalyst compound comprises a compound according to Formula III,        Formula III being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹ and N² are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²¹            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;        -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or            R²⁰ comprise fluorine; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

    -   P. The process of embodiment O, wherein in the catalyst compound        according to Formula III, one or more of R¹, R², R³, R⁴, R⁵, R⁶,        R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        R²⁰, R²¹, and R²² is a methyl radical, a fluoride, or a        combination thereof.

    -   Q. The process of embodiment O or embodiment P, wherein in the        catalyst compound according to Formula III:        -   M is Ti;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹¹ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰            are fluorine; and        -   Y is —CH₂CH₂—.

    -   R. The process of embodiment O or embodiment P, wherein in the        catalyst compound according to Formula III:        -   M is Ti;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹¹ and R¹⁴ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are            fluorine; and        -   Y is —CH₂CH₂—.

    -   S. The process of embodiment O or embodiment P, wherein in the        catalyst compound according to Formula III:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹¹ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰            are fluorine; and        -   Y is —CH₂CH₂—.

    -   T. The process of embodiment O or embodiment P, wherein in the        catalyst compound according to Formula III:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹¹ and R¹⁴ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are            fluorine; and        -   Y is —CH₂CH₂—.

    -   U. The process of any one of embodiments C to T, wherein two or        more of R¹ to R²⁸ of Formula I if present, R¹ to R²¹ of Formula        II if present, R¹ to R²² of Formula III if present, or a        combination thereof, independently join together to form a C₄ to        C₆₂ cyclic or polycyclic ring structure.

    -   V. The process of any one of embodiments C to U, wherein M of        Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is Hf, Ti, or Zr.

    -   W. The process of any one of embodiments C to V, wherein each X        of Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is, independently, a halogen        or a C₁ to C₇ hydrocarbyl radical.

    -   X. The process of any one of embodiments C to W, wherein each X        of Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is a benzyl radical.

    -   Y. The process of any one of embodiments C to X, wherein each        R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,        R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷        and R²⁸ of Formula I if present, each R¹, R², R³, R⁴, R⁵, R⁶,        R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        R²⁰, and R²¹ of Formula II if present, R¹, R², R³, R⁴, R⁵, R⁶,        R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        R²⁰, R²¹, and R²² of Formula III if present, or a combination        thereof are, independently, hydrogen, a halogen, or a C₁ to C₃₀        hydrocarbyl radical.

    -   Z. The process of any one of embodiments C to Y, wherein each        R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,        R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵, R²⁶, R²⁷        and R²⁸ of Formula I if present, each R¹, R², R³, R⁴, R⁵, R⁶,        R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        R²⁰, and R²¹ of Formula II if present, R¹, R², R³, R⁴, R⁵, R⁶,        R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹,        R²⁰, R²¹, and R²² of Formula III if present, or a combination        thereof are, independently, hydrogen, a halogen, or a C₁ to C to        hydrocarbyl radical.

    -   A1. The process of any one of embodiments C to Z, wherein Y of        Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is —CH₂CH₂— or        1,2-cyclohexylene.

    -   B1. The process of any one of embodiments C to A1, wherein Y of        Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is —CH₂CH₂CH₂—.

    -   C1. The process of any one of embodiments C to B1, wherein Y of        Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is a C₁-C₄₀ divalent        hydrocarbyl radical comprising a linker backbone comprising from        1 to 18 carbon atoms bridging between nitrogen atoms N¹ and N².

    -   D1. The process of any one of embodiments C to C1, wherein Y of        Formula I if present, Formula II if present, Formula III if        present, or a combination thereof is a C₁-C₄₀ divalent        hydrocarbyl radical comprising O, S, S(O), S(O)₂, Si(R′)₂,        P(R′), N, N(R′), or a combination thereof, wherein each R′ is        independently a C₁-C₁₈ hydrocarbyl radical.

    -   E1. The process of any one of embodiments A to D1, wherein the        activator comprises alumoxane, an alkylalumoxane, or a        combination thereof.

    -   F1. The process of any one of embodiments A to E1, wherein the        activator comprises alumoxane, methylalumoxane, or a combination        thereof, and wherein the activator is present at a ratio of 1        mole aluminum or more to mole of catalyst compound.

    -   G1. The process of any one of embodiments A to F1, wherein the        activator comprises trimethylaluminum-depleted alkylalumoxane.

    -   H1. The process of any one of embodiments A to G1, wherein the        activator comprises trimethylaluminum-depleted methylalumoxane.

    -   I1. The process of any one of embodiments A to H1, wherein the        activator is methylalumoxane supported on an inorganic oxide        comprising an element from Group 2, 4, 13, 14 of the periodic        table, or a combination thereof.

    -   J1. The process of any one of embodiments A to I1, wherein the        activator is methylalumoxane supported on silica, alumina,        magnesia, titania, zirconia, montmorillonite, phyllosilicate,        zeolite, talc, clay, or a combination thereof.

    -   K1. The process of any one of embodiments A to J1, wherein the        activator is methylalumoxane supported on fumed silica.

    -   L1. The process of any one of embodiments A to K1, wherein the        activator, the catalyst compound, or a combination thereof is        supported using incipient wetness.

    -   M1. The process of any one of embodiments A to L1, wherein the        activator, the catalyst compound, or a combination thereof is        supported by contacting the activator, the catalyst compound, or        both with a support to form a supported activator, supported        catalyst, or a combination thereof, wherein the activator, the        catalyst compound, or a combination thereof are deposited on,        vaporized with, bonded to, incorporated within, adsorbed or        absorbed in, or on, the support.

    -   N1. The process of any one of embodiments A to L1, wherein the        temperature is from about 0° C. to about 300° C., the pressure        is from about 0.35 MPa to about 10 MPa, the time is from about        0.1 minutes to about 24 hours, or a combination thereof, and/or        wherein the temperature is from about 50° C. to about 150° C.

    -   O1. The polyolefin obtained by the process of any one of        embodiments A to N1.

    -   P1. A polyolefin comprising ethylene, wherein the polyolefin is        produced by a process comprising:        -   contacting one or more olefins with a catalyst system at a            temperature, a pressure, and for a period of time sufficient            to produce a polyolefin, the catalyst system comprising an            activator and a catalyst compound disposed on a support;        -   the catalyst compound according to Formula I, Formula II,            Formula III, or a combination thereof:        -   Formula I being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², N³ and N⁴ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,            R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            two or more of R¹ to R²⁸ may independently join together to            form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a            combination thereof; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl;        -   Formula II being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², and N³ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²¹            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;            subject to the proviso that R¹⁹ is not a carbazole or a            substituted carbazole radical, and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;        -   Formula III being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   wherein M is a Group 3, 4, 5 or 6 transition metal;        -   N¹ and N² are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²²            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;        -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or            R²⁰ comprise fluorine; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

    -   Q1. The polyolefin of embodiment O1 or embodiment P1, wherein        the polyolefin comprises a vinyl content of at least 50%, based        upon total unsaturation, as determined by ¹H NMR.

    -   R1. The polyolefin of any one of embodiments O1 to Q1, wherein        the polyolefin comprises at least 80% vinyl termination as        determined by ¹H NMR.

    -   S1. The polyolefin of any one of embodiments O1 to R1,        comprising at least 50 mole % ethylene.

    -   T1. The polyolefin of any one of embodiments O1 to R1,        comprising at least 75 mole % ethylene.

    -   U1. The polyolefin of any one of embodiments O1 to R1,        comprising at least 99.9 mole % ethylene.

    -   V1. The polyolefin of any one of embodiments O1 to U1,        comprising:        -   a) a ratio of saturated chain ends to allyl chain ends of            greater than 1:1;        -   b) a ratio of vinyl groups per molecule as determined by ¹³C            NMR of at least 50%; and        -   c) an Mn of at least 250 g/mol as determined by ¹H NMR; or a            combination thereof.

    -   W1. The polyolefin of any one of embodiments O1 to V1,        comprising an Mn of 250 g/mol to 100,000 g/mol.

    -   X1. The polyolefin of any one of embodiments O1 to W1, further        comprising propylene.

    -   Y1. A catalyst system comprising an activator and a catalyst        compound disposed on a support, according to Formula I, Formula        II, Formula III, or a combination thereof;        -   Formula I being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², N³ and N⁴ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴, R²⁵,            R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            two or more of R¹ to R²⁸ may independently join together to            form a C₄ to C₆₂ cyclic or polycyclic ring structure, or a            combination thereof, or a combination thereof; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl;        -   Formula II being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   M is a Group 3, 4, 5 or 6 transition metal;        -   N¹, N², and N³ are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²¹            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;            subject to the proviso that R¹⁹ is not a carbazole or a            substituted carbazole radical, and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical;        -   Formula III being represented by:

-   -   -   wherein each solid line represents a covalent bond and each            dashed line represents a bond having varying degrees of            covalency and a varying degree of coordination;        -   M is a Group 3, 4, 5 or 6 transition metal;        -   N¹ and N² are nitrogen;        -   O is oxygen;        -   each of X¹ and X² is, independently, a univalent C₁ to C₂₀            hydrocarbyl radical, a functional group comprising elements            from Groups 13-17 of the periodic table of the elements, or            X¹ and X² join together to form a C₄ to C₆₂ cyclic or            polycyclic ring structure, provided however when M is            trivalent X² is not present;        -   each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,            R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is,            independently, a hydrogen, a C₁-C₄₀ hydrocarbyl radical, a            functional group comprising elements from Group 13-17 of the            periodic table of the elements, or two or more of R¹ to R²¹            may independently join together to form a C₄ to C₆₂ cyclic            or polycyclic ring structure, or a combination thereof;        -   at least one of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or            R²⁰ comprise fluorine; and        -   Y is a divalent C₁ to C₂₀ hydrocarbyl radical.

    -   Z1. The catalyst system of embodiment Y1, wherein two or more of        R¹ to R²⁸ of Formula I, R¹ to R²¹ of Formula II, R¹ to R²² of        Formula III, or a combination thereof, independently join        together to form a C₄ to C₆₂ cyclic or polycyclic ring        structure.

    -   A2. The catalyst system according to any one of embodiments Y1        or Z1, wherein M of Formula I, Formula II, Formula III, or a        combination thereof is Hf, Ti, or Zr.

    -   B2. The catalyst system according to any one of embodiments Y1        to A2, wherein each X of Formula I, Formula II, Formula III, or        a combination thereof is, independently, a halogen or a C₁ to C₇        hydrocarbyl radical.

    -   C2. The catalyst system according to any one of embodiments Y1        to B2, wherein each X of Formula I, Formula II, Formula III, or        a combination thereof is a benzyl radical.

    -   D2. The catalyst system according to any one of embodiments Y1        to C2, wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,        R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³        R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ of Formula (I), each R¹, R², R³, R⁴,        R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,        R¹⁹, R²⁰, and R²¹ of Formula (II), R¹, R², R³, R⁴, R⁵, R⁶, R⁷,        R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,        R²¹, and R²² of Formula (III), or a combination thereof are,        independently, hydrogen, a halogen, or a C₁ to C₃₀ hydrocarbyl        radical.

    -   E2. The catalyst system according to any one of embodiments Y1        to D2, wherein each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,        R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³        R²⁴, R²⁵, R²⁶, R²⁷ and R²⁸ of Formula (I), each R¹, R², R³, R⁴,        R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸,        R¹⁹, R²⁰, and R²¹ of Formula (II), R¹, R², R³, R⁴, R⁵, R⁶, R⁷,        R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰,        R²¹, and R²² of Formula (III), or a combination thereof are,        independently, hydrogen, a halogen, or a C₁ to C₁₀ hydrocarbyl        radical.

    -   F2. The catalyst system according to any one of embodiments Y1        to E2, wherein one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸,        R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹,        R²², R²³ R²⁴, R²⁵, R²⁶, R²⁷, and R²⁸ of Formula I is a methyl        radical, a fluoride, or a combination thereof.

    -   G2. The catalyst system according to any one of embodiments Y1        to F2, wherein the catalyst compound is according to Formula I,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R² through R¹³ and R¹⁵ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   H2. The catalyst system according to any one of embodiments Y1        to G2, wherein the catalyst compound is according to Formula I,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are            hydrogen; and        -   Y is —CH₂CH₂—.

    -   I2. The catalyst system according to any one of embodiments Y1        to H2, wherein the catalyst compound is according to Formula I,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R⁴ and R¹⁷ are fluoro groups;        -   R², R³, R⁵ through R¹³, R¹⁵, R¹⁶, R¹⁸ through R²⁸ are            hydrogen; and        -   Y is —CH₂CH₂—.

    -   J2. The catalyst system according to any one of embodiments Y1        to 12, wherein the catalyst compound is according to Formula I,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R⁸, R¹¹, R²¹ and R²⁴ are tert-butyl radicals;        -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,            R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   K2. The catalyst system according to any one of embodiments Y1        to J2, wherein the catalyst compound is according to Formula I,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹⁴ and R¹⁷ are methyl radicals;        -   R⁸, R¹¹, R²¹ and R²⁴ are mesityl radicals;        -   R², R³, R⁵, R⁶, R⁷, R⁹, R¹⁰, R¹², R¹³, R¹⁵, R¹⁶, R¹⁸, R¹⁹,            R²⁰, R²², R²³, R²⁵ and R²⁶ through R²⁸ are hydrogen; and        -   Y is —CH₂CH₂—.

    -   L2. The catalyst system according to any one of embodiments Y1        to K2, wherein the catalyst compound is according to Formula II,        wherein one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,        R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is a        methyl radical, a bromide, an adamantyl radical, or a        combination thereof.

    -   M2. The catalyst system according to any one of embodiments Y1        to L2, wherein the catalyst compound is according to Formula II,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;        -   R¹⁷ and R¹⁹ are bromine; and        -   Y is —CH₂CH₂—.

    -   N2. The catalyst system according to any one of embodiments Y1        to M2, wherein the catalyst compound is according to Formula II,        wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R¹⁴ and R¹⁷ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰, and R²¹ are hydrogen;        -   R¹⁹ is a 1-adamantyl radical; and        -   Y is —CH₂CH₂—.

    -   O2. The catalyst system according to any one of embodiments Y1        to N2, wherein the catalyst compound is according to Formula II,        wherein:        -   M is Hf;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹⁴ and R¹⁷ are methyl radicals;        -   R² through R¹³, R¹⁵, R¹⁶, R¹⁸, R²⁰ and R²¹ are hydrogen;        -   R¹⁹ is a 1-adamantyl radical; and        -   Y is —CH₂CH₂—.

    -   P2. The catalyst system according to any one of embodiments Y1        to O2, wherein the catalyst compound is according to Formula        III, wherein one or more of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹,        R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and        R²² is a methyl radical, a fluoride, or a combination thereof.

    -   Q2. The catalyst system according to any one of embodiments Y1        to P2, wherein the catalyst compound is according to Formula        III, wherein:        -   M is Ti;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹¹ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰            are fluorine; and        -   Y is —CH₂CH₂—.

    -   R2. The catalyst system according to any one of embodiments Y1        to Q2, wherein the catalyst compound is according to Formula        III, wherein:        -   M is Ti;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹¹ and R¹⁴ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are            fluorine; and        -   Y is —CH₂CH₂—.

    -   S2. The catalyst system according to any one of embodiments Y1        to R2, wherein the catalyst compound is according to Formula        III, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹ and R¹¹ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁴, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰            are fluorine; and        -   Y is —CH₂CH₂—.

    -   T2. The catalyst system according to any one of embodiments Y1        to S2, wherein the catalyst compound is according to Formula        III, wherein:        -   M is Zr;        -   X¹ and X² are benzyl radicals;        -   R¹, R⁴, R¹¹ and R¹⁴ are methyl radicals;        -   R², R³, R⁵, R¹², R¹³, R¹⁵, R²¹ and R²² are hydrogen;        -   R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰ are            fluorine; and        -   Y is —CH₂CH₂—.

    -   U2. The catalyst system according to any one of embodiments Y1        to T2, wherein Y of Formula I, Formula II, Formula III, or a        combination thereof is —CH₂CH₂— or 1,2-cyclohexylene.

    -   V2. The catalyst system according to any one of embodiments Y1        to U2, wherein Y of Formula I, Formula II, Formula III, or a        combination thereof is —CH₂CH₂CH₂—.

    -   W2. The catalyst system according to any one of embodiments Y1        to V2, wherein Y of Formula I, Formula II, Formula III, or a        combination thereof is a C₁-C₄₀ divalent hydrocarbyl radical        comprising a linker backbone comprising from 1 to 18 carbon        atoms bridging between nitrogen atoms N¹ and N².

    -   X2. The catalyst system according to any one of embodiments Y1        to W2, wherein Y of Formula I, Formula II, Formula III, or a        combination thereof is a C₁-C₄₀ divalent hydrocarbyl radical        comprising O, S, S(O), S(O)₂, Si(R′)₂, P(R′), N, N(R′), or a        combination thereof, wherein each R′ is independently a C₁-C₁₈        is hydrocarbyl radical.

    -   Y2. The catalyst system according to any one of embodiments Y1        to X2, wherein the activator comprises alumoxane, an        alkylalumoxane, or a combination thereof.

    -   Z2. The catalyst system according to any one of embodiments Y1        to Y2, wherein the activator comprises alumoxane,        methylalumoxane, or a combination thereof, and wherein the        activator is present at a ratio of 1 mole aluminum or more to        mole of catalyst compound.

    -   A3. The catalyst system according to any one of embodiments Y1        to Z2, wherein the activator comprises        trimethylaluminum-depleted alkylalumoxane.

    -   B3. The catalyst system according to any one of embodiments Y1        to A3, wherein the activator comprises        trimethylaluminum-depleted methylalumoxane.

    -   C3. The catalyst system according to any one of embodiments Y1        to B3, wherein the activator is methylalumoxane supported on an        inorganic oxide comprising an element from Group 2, 4, 13, 14 of        the periodic table, or a combination thereof.

    -   D3. The catalyst system according to any one of embodiments Y1        to C3, wherein the activator is methylalumoxane supported on        silica, alumina, magnesia, titania, zirconia, montmorillonite,        phyllosilicate, zeolite, talc, clay, or a combination thereof.

    -   E3. The catalyst system according to any one of embodiments Y1        to D3, wherein the activator is methylalumoxane supported on        fumed silica.

    -   F3. The catalyst system according to any one of embodiments Y1        to E3, wherein the activator, the catalyst compound, or a        combination thereof is supported using incipient wetness.

    -   G3. The catalyst system according to any one of embodiments Y1        to F3, wherein the activator, the catalyst compound, or a        combination thereof is supported by contacting the activator,        the catalyst compound, or both with a support to form a        supported activator, supported catalyst, or a combination        thereof, wherein the activator, the catalyst compound, or a        combination thereof are deposited on, vaporized with, bonded to,        incorporated within, adsorbed or absorbed in, or on, the        support.

EXAMPLES

The foregoing discussion can be further described with reference to thefollowing non-limiting examples. Four illustrative catalyst compounds(A, B, C and D), each according to one or more embodiments described,were synthesized and some were used to polymerize olefins. All reactionswere carried out under a purified nitrogen atmosphere using standardglovebox, high vacuum or Schlenk techniques, unless otherwise noted. Allsolvents used were anhydrous, de-oxygenated and purified according toknown procedures. All starting materials were either purchased fromAldrich and purified prior to use or prepared according to proceduresknown to those skilled in the art.

Synthesis of Compounds A-D

9-(2-Methoxy-5-methylphenyl)-9H-carbazole (1)

2-Bromo-4-methylanisole (20.11 g, 100 mmol, 1 equiv) and carbazole(20.06 g, 120 mmol, 1.2 equiv) were dissolved in 1,4-dioxane (400 mL).Potassium phosphate tribasic (37.15 g, 175 mmol, 1.75 equiv), copper (I)iodide (0.95 g, 5 mmol, 0.05 equiv) and racemictrans-1,2-diaminocyclohexane (2.4 mL, 20 mmol, 0.2 equiv) were added andthe reaction was refluxed for two days. The reaction was cooled to roomtemperature, then partitioned with ethyl acetate (200 mL) and water (300mL). The aqueous layer was extracted with ethyl acetate (3×200 mL). Thecombined organic layers were washed with saturated brine, dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (150 g), eluting with 3% ethylacetate in heptanes to give compound 1 (13.5 g, 45% yield) as a yellowsolid.

2-(9H-Carbazol-9-yl)-4-methylphenol (2)

A 1.0 m boron tribromide solution in dichloromethane (90 mL, 90 mmol,1.9 equiv) was added drop wise at −78° C., over 30 minutes, to asolution of compound 1 (13.5 g, 46.98 mmol, 1 equiv) in anhydrousdichloromethane (400 mL). The reaction was warmed to room temperature,when liquid chromatography-mass spectrometry (LCMS) indicated that thereaction was complete. The reaction was quenched with ice-water (200mL). The layers were separated and the aqueous phase was extracted withdichloromethane (2×100 mL). The combined organic layers were dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified on an ANALOGIX 40-150 g column, eluting with agradient of 0 to 20% ethyl acetate in heptanes to give compound 2 (12.3g, 95% yield) as a yellow oil.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-methylphenol)(3)

A mixture of compound 2 (3.4 g, 12.44 mmol, 2 equiv), paraformaldehyde(1.87 g, 62.2 mmol, 10 equiv), N,N′-dimethylethylenediamine (0.67 mL,6.22 mmol, 1 equiv) and anhydrous ethanol (100 mL) was refluxed for 18hours. The reaction was cooled to room temperature, and thenconcentrated under reduced pressure. The residue was purified on anANALOGIX 25-60 g column, eluting with a gradient of 0 to 30% ethylacetate in heptanes to give compound 3 (1.1 g, 27% yield) as a whitesolid.

9-(5-Fluoro-2-methoxyphenyl)-9H-carbazole (4)

2-Bromo-4-fluoroanisole (20 g, 10 mmol, 1 equiv) and carbazole (18.4 g,11 mmol, 1.1 equiv) were dissolved in 1,4-dioxane (200 mL). Potassiumphosphate tribasic hydrate (46 g, 20 mmol, 2 equiv), copper(I) iodide (1g, 0.5 mmol, 0.05 equiv) and 1,2-diaminopropane (1 mL, 1.3 mmol, 0.13equiv) were added and the reaction was refluxed for 18 hours. Thereaction was cooled to room temperature and filtered through CELITEdiatomaceous earth. The filtrate was concentrated under reduced pressureand the residue was purified over silica gel (250 g), eluting withgradient of 0 to 10% ethyl acetate in heptanes to give compound 4 (7.6g, 26% yield) as an off white solid that was contaminated withcarbazole. This material was used subsequently.

2-(9H-Carbazol-9-yl)-4-fluorophenol (5)

A 1.0 M boron tribromide solution in dichloro-methane (60 mL, 60 mmol, 3equiv) was added drop wise over 30 minutes at −78° C. to a solution ofcompound 4 (5.8 g, 20 mmol, 1 equiv) in dichloromethane (60 mL). Thereaction was stirred at −78° C. for 4 hours, when ¹H-NMR indicated thatthe reaction was complete. The reaction was poured into saturated sodiumbicarbonate (100 mL) and the pH adjusted to 8 with 10% sodium hydroxide.The layers were separated and the aqueous phase was extracted withdichloro-methane (3×20 mL). The combined organic layers were dried oversodium sulfate, filtered, and concentrated under reduced pressure. Theresidue was purified over silica gel (100 g), eluting with a gradient of60 to 100% dichloromethane in heptanes. The product containing fractionswere combined, concentrated under reduced pressure and triturated with20% methyl tert-butyl ether in heptanes (10 mL) to give compound 5 (4.3g, 78% yield) as a white solid.

6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-fluorophenol)(6)

A mixture of compound 5 (1.5 g, 5.4 mmol, 2 equiv), paraformaldehyde(716 mg, 5.4 mmol, 2 equiv), N,N′-dimethylethylenediamine (300 μL, 2.7mmol, 1 equiv) and anhydrous ethanol (20 mL) was refluxed for 18 hours(reaction was 60% complete after 2 hours). The reaction was cooled toroom temperature, then concentrated under reduced pressure. The residuewas purified over silica gel (50 g), eluting with a gradient of 60 to100% dichloromethane in heptanes to give compound 6 (640 mg, 34% yield)as a white solid.

2-(9H-carbazol-9-yl)-6-(1,3-dimethylimidazolidin-2-yl)phenol (7)

In a 100 mL round bottom flask, 2-(9H-carbazol-9-yl)salicylaldehyde(0.573 g, 2.06 mmol) was dissolved in 30 mL of methanol and heated to50° C. Ethylenediamine (0.176 g, 2.00 mmol) was also dissolved in 10 mLof methanol. When all of the 2-(9H-carbazol-9-yl)salicylaldehyde wasdissolved, the solution of ethylene diamine was slowly added. After twohours, the flask was removed from the heat source and allowed to coolovernight. A precipitate was collected and used in the next step withoutfurther purification.

2-(9H-carbazol-9-yl)-6-((methyl(2-(methylamino)ethyl)amino)methyl)phenol(8)

A slurry of 7 from the previous synthesis was stirred at roomtemperature in a 100 mL round bottom flask. Sodium borohydride (0.640 g,16.9 mmol) was added in small portions over 30 minutes. Gas evolutionwas observed. After three hours, the methanol was removed under vacuumand water was added. The resulting solids were filtered and washed withcold methanol. The white solids were dried under vacuum to yield 8(0.585 g, 79% yield).

2-(((2-((3-(9H-carbazol-9-yl)-2-hydroxybenzyl)(methyl)amino)ethyl)(methyl)-amino)methyl)-4,6-dibromophenol(9)

8 (0.218 g, 0.606 mmol) and 2-bromomethyl-4,6-dibromophenol (0.209 g,0.606 mmol) were dissolved in 20 mL of THF. Triethylamine (1.2 mL, 8.61mmol) was added to the slightly pink solution. A white precipitateformed immediately. The reaction was allowed to stir overnight afterwhich time the volatiles were removed and methanol added to make aslurry. The solids were filtered and dried under vacuum resulting in awhite solid (0.215 g, 57% yield).

2-(2-Methoxy-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(10)

To a solution of 2-bromo-4-methylanisole (10 g, 50 mmol, 1 equiv) in1,4-dioxane (300 mL) was added bis(pinacolato)diboron (14 g, 55 mmol,1.1 equiv), potassium acetate (17.2 g, 175 mmol, 3.5 equiv) and1,1′-bis(diphenylphosphino)ferrocene (DPPF, 1.39 g, 2.5 mmol, 0.05equiv) at room temperature. The resulting mixture was sparged withnitrogen for 10 minutes.1,1′-Bis(diphenyl-phosphino)ferrocenedichloropalladium DCM adduct (1.92g, 2.5 mmol, 0.05 equiv) was added and the resulting mixture was spargedwith nitrogen for additional 5 minutes. The mixture was refluxedovernight. After the mixture was cooled to room temperature, dilutedwith ethyl acetate (300 mL) and washed by water (200 mL). The aqueouslayer was extracted with ethyl acetate (2×200 mL). The combined organiclayers were washed with saturated brine, dried over sodium sulfate,filtered, and concentrated under reduced pressure. The residue waspurified over silica gel (500 g), eluting with a gradient of 0 to 15%ethyl acetate in heptanes to give2-(2-methoxy-5-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(10) (11.3 g, 91% yield) as yellow solid.

2,3,4,5,6-Pentafluoro-2′-methoxy-5′-methyl-1,1′-biphenyl (11)

Compound 10 (11.3 g, 45.54 mmol, 1 equiv) and iodopentafluorobenzene(10.6 g, 36.2 mmol, 1 equiv) were dissolved in toluene (200 mL) and 1.0Mpotassium carbonate solution (200 mL). Tetrabutylammonium bromide (1.6g, 5 mmol, 0.11 equiv) was added and the solution sparged with nitrogenfor 10 minutes. Tetrakis(triphenylphosphine)palladium(0) (2.63 g, 2.28mmol, 0.05 equiv) was added and the reaction was refluxed for one day.The reaction was cooled to room temperature, then the layers wereseparated. The aqueous phase was back extracted with ethyl acetate(2×200 mL). Combined organic phases were combined, dried over sodiumsulfate and concentrated under reduced pressure. The residue waspurified over silica gel (200 g), eluting with heptanes to give2,3,4,5,6-pentafluoro-2′-methoxy-5′-methyl-1,1′-biphenyl (11) (9.7 g,74% yield) as a pale-yellow oil. This material contained a small amountof unreacted iodopentafluorobenzene which was identified by ¹⁹F NMR. Thematerial was used subsequently.

2′,3′,4′,5′,6′-Pentafluoro-5-methyl-[1,1′-biphenyl]-2-ol (12)

A 1.0 M boron tribromide solution in dichloromethane (67.3 mL, 67.3mmol, 2 equiv) was added drop wise, at −78° C., over 30 minutes to asolution of compound 11 (9.7 g, 33.65 mmol, 1 equiv) in anhydrousdichloro-methane (300 mL). The reaction was warmed to room temperature,when LCMS indicated that the reaction was complete. The reaction wasquenched with ice-water (200 mL). The layers were separated and theaqueous phase was extracted with dichloromethane (2×100 mL). Thecombined organic layers were dried over sodium sulfate, filtered, andconcentrated under reduced pressure. The residue was purified on anAnaLogix 65-200 g column, eluting with a gradient of 0 to 20% ethylacetate in heptanes to give2′,3′,4′,5′,6′-pentafluoro-5-methyl-[1,1′-biphenyl]-2-ol (12) (8.15 g,88% yield) as a light-brown oil.

3,3″-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2′,3′,4′,5′,6′-pentafluoro-5-methyl-[1,1′-biphenyl]-2-ol)(13)

A mixture of compound 12 (8.15 g, 29.7 mmol, 2 equiv), paraformaldehyde(4.46 g, 148.5 mmol, 10 equiv), N,N′-dimethylethylenediamine (1.6 mL,14.85 mmol, 1 equiv) and anhydrous ethanol (100 mL) was refluxed for 2hours. LCMS indicated that the reaction was complete. The reaction wascooled to room temperature and concentrated under reduced pressure. Theresidue was purified on an AnaLogix 65-200 g column, eluting with agradient of 0 to 30% ethyl acetate in heptanes to give3,3″-((ethane-1,2-diylbis(methyl-azanediyl))bis(methylene))bis(2′,3′,4′,5′,6′-pentafluoro-5-methyl-[1,1′-biphenyl]-2-ol)(12) (5.0 g, 51% yield) as a white solid.

9-(2-Methoxy-5-methylphenyl)-9H-(3,6-di-tert-butyl-carbazole) (13)

Racemic trans-1,2-diaminocyclohexane (5.12 mL, 42.6 mmol, 0.2 equiv),potassium phosphate tribasic (79.2 g, 372 mmol, 1.75 equiv) andcopper(I) iodide (2.03 g, 10.7 mmol, 0.05 equiv) were added at roomtemperature to a mixture of 2-bromo-4-methylanisole (42.9 g, 213 mmol,1.0 equiv) and 3,6-di-tert-butyl-9H-carbazole (65.5 g, 234 mmol, 1.1equiv) in 1,4-dioxane (1000 mL), which was degassed with a stream ofnitrogen for 15 minutes. The mixture was refluxed for four days, atwhich point LCMS indicated 40% conversion to product. After cooling toroom temperature, the mixture was diluted with water (500 mL) and ethylacetate (1000 mL). The layers were separated and the aqueous layer wasextracted with ethyl acetate (3×500 mL). The combined organic layerswere washed with saturated brine (500 mL), dried over sodium sulfate,filtered, and concentrated under reduced pressure. The crude product wastriturated with a 1:1 mixture of methyl tert-butyl ether and heptanes(500 mL) to give pure product. The mother liquor was purified on aBIOTAGE-75L column, eluting with a gradient of 5 to 10% ethyl acetate inheptanes to give additional pure product. The two batches were combinedto give compound 13 (34.5 g, 37% yield) as an off-white solid.

2-(9H-(3,6-di-tert-butyl-Carbazol-9-yl))-4-methylphenol (14)

1.0M boron tribromide in dichloromethane (173 mL, 173 mmol, 2.0 equiv)was added drop wise at −70° C. to a solution of compound 13 (34.5 g,86.5 mmol, 1.0 equiv) in anhydrous dichloromethane (700 mL). The mixturewas allowed to warm to room temperature at which point LCMS indicatedthat the reaction was complete. The reaction was quenched by the slowaddition of ice-water (200 mL) and the layers were separated. Theaqueous layer was extracted with dichloromethane (2×200 mL), and thecombined organic layers were washed with saturated brine (200 mL), driedover sodium sulfate, filtered, and concentrated under reduced pressure.The residue was purified over silica gel (500 g) with dry-loading,eluting with a gradient of 0 to 20% ethyl acetate in heptanes to givethe desired product (31 g, 85% purity) as an off-white solid. Thismaterial was triturated with 5% ethyl acetate in heptanes (100 mL) togive compound 14 (18.9 g) as a white solid.

6,6-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-(3,6-di-tert-butyl-carbazol-9-yl))-4-methylphenol)(15)

compound 14 (2.07 g; 5.37 mmol), N,N′-dimethylethylenediamine (0.144 mL,0.118 g, 1.63 mmol) and paraformaldehyde (0.161 g, 5.36 mmol) weredissolved in 40 mL of ethanol and refluxed overnight. The reactionmixture was allowed to cool to room temperature. The volatiles wereremoved under vacuum to give a pale yellow solid. Flash chromatographyusing a gradient of 40-100% dichloromethane/hexanes yielded compound 15(0.95 g) as an off-white solid (40% yield).

[6,6′-((Ethane-1,2-diylbis(methylazanediyl))bis(methylene))bis(2-(9H-carbazol-9-yl)-4-methylphenol)]zirconium(IV)dibenzyl(A)

Under a nitrogen atmosphere, a toluene solution (5 mL) of 3 (107 mg,0.17 mmol) was added to a yellow toluene solution (5 mL) of ZrBn₄ (77mg, 0.17 mmol), forming a deep yellow solution. After stirring at roomtemperature for 15 minutes, the solvent was removed to give a yellowsticky solid. The product was washed with pentane and dried under vacuumto give compound A as a yellow solid (yield 135 mg, 88%). Compounds Bthrough F were made in a similar manner from compounds 6, 9, 3, 13, or15 and the corresponding Group IV tetrabenzyl precursors.

All reactions were performed under an inert nitrogen atmosphere.Solvents were anhydrous grade from Sigma Aldrich which were sparged withnitrogen and stored over alumina beads (activated at 300° C.) beforeuse. Deuterated solvents were obtained from Cambridge IsotopeLaboratories (Andover, Mass.) and dried over 3 Å molecular sieves. Allother reagents were obtained from Sigma Aldrich (St. Louis, Mo.) andused as received, unless otherwise noted. All ¹H NMR data were collectedon a Broker AVANCE III 400 MHz spectrometer running Topspin™ 3.0software at room temperature (approx. 23° C.). Tetrachloroethane-d₂ wasused as a solvent (chemical shift of 5.98 ppm was used as a reference)for all materials.

Methyl Alumoxane Supported on Silica (SMAO):

In a celstir flask a 13.8 gram amount of Grace 948 silica that waspreviously calcined at 600° C. was slurried in 110 mL of toluene andheated to 80° C. MAO (30% by weight in toluene) (23.5152 g solution) wasslowly added to the slurry. The slurry was stirred for 1 hr before beingfiltered and washed 4 times with 50 mL of toluene and dried undervacuum. 19.9883 g of a white solid was collected.

Representative Sample for Slurry SMAO Preparation:

Catalyst B (25.2 mg) was dissolved in 5 mL of toluene. This solution wasadded to a slurry of SMAO (0.822 g) in 25 mL of toluene. After 1 hr theslurry was filtered leaving a pale yellow solid that is washed withtoluene and dried under vacuum. Collected 0.764 g of a pale yellowsolid.

Slurry SMAO catalyst preparations Supported catalyst Catalyst (mg) SMAO(g) Yield (g) A/SMAO 30.8 0.8832 0.8526 B/SMAO 25.2 0.822 0.764 C/SMAO27.3 0.7619 0.6932 E/SMAO 30.0 0.8066 0.7375Representative Sample for Incipient Wetness MAO-Silica Preparation

In a 20 mL vial, MAO (30% by weight in toluene) (0.5984 g solution) wasallowed to stir for 15 min with an additional 1 mL of toluene. CatalystC (28.4 mg) was then added as a solid and allowed to stir for anadditional 15 min. To this was added 948 Silica (0.7932 g) previouslycalcined at 600° C. The mixture was stirred via spatula for 10 min toreach a uniform pale yellow color. The solid was placed under vacuum.Collected 0.9539 g of a pale yellow solid.

Supported Catalyst catalyst (mg) MAO** (g) 948 Silica (g) Yield (g) C/I*28.4 0.5984 0.7932 0.9539 A/I* 25.7 0.6085 0.6909 0.8535 F/I* 24.70.5056 0.4095 0.5537 *I—incipient wetness **solutionPreparation of Supported Methylalumoxane (SMAO-2)

Toluene (80 ml) and MAO (Albemarle, 30 wt % in toluene, 37.49 g, 194mmol Al) were combined. Then Davidson 948 silica (30 g), which had beencalcined at 600° C., was added. The mixture was heated to 100° C. andthe mixture was swirled occasionally. After 3 hours the mixture wascooled to ambient temperature and the solids were collected on a glassfritted disk. The product was dried under reduced pressure for 22 hoursto afford a free-flowing white solid (40.5 g).

Preparation of Catalyst D/SMAO-2

A toluene (5 mL) solution of catalyst compound D (0.0500 g, 0.0491 mmol)was combined with SMAO-2 (1.23 g, 5.89 mmol Al). The mixture wasswirled. After 5 minutes the solids were collected on a glass frit,washed with toluene (3×5 mL), and dried under reduced pressure to afforda white powder (1.26 g).

Preparation of Catalyst B/SMAO-2

A toluene (5 mL) solution of catalyst compound B (0.0482 g, 0.0514 mmol)was combined with SMAO-2 (1.29 g, 6.16 mmol Al). The mixture wasswirled. After 5 minutes the solids were collected on a glass frit,washed with toluene (3×5 mL), and dried under reduced pressure to afforda pale yellow powder (1.33 g).

General Procedure for Ethylene Polymerizations

Semi-continuous ethylene polymerizations were performed in a stirred 1 Lautoclave reactor. Details of polymerization conditions and the productsformed are described in Table 1. All solvents, reactants, and gases werepurified by passing through multiple columns containing 3 angstrommolecular sieves and oxygen scavenger. Typically, isohexane (500 mL) andscavenger (tri-n-octylaluminum, 0.10 mmol) was added to the reactor andthe mixture was heated to the desired temperature. The reactor was thenpressurized with ethylene to a pressure 137.9 kPa to 241.3 kPa (20-35psi) below the final reaction pressure. Once the reactor hadequilibrated a slurry of the catalyst in toluene (2 mL) was pushed inwith ethylene gas at the final reaction pressure. Polymerization wascarried out for a set amount of time and then the reactor was cooled,depressurized, and opened. The residual volatiles in the product wereremoved under a stream of nitrogen, followed by heating the sample in avacuum oven at 60° C.

TABLE 1 Summary of polymerization conditions and data C₂ Activity NMR %Complex Catalyst/ (kPa T Time Yield A (g/ (g pol/ NMR % internal NMR Run(nmol) Activator (psi)) (° C.) (min) (g) mmol) g⁻cat.*hr) vinylvinylidene Mn 1 8000 D/SMAO-2 1380 (200) 65 20 36.9 4613 — 90.1 9.922,753 2 8000 D/SMAO-2 1380 (200) 65 60 94.6 11821 — 100.0.  0.0 25,6903 6000 D/SMAO-2 15200 (2200) 80 60 126.9 21150 — 100.0.  0.0 23,476 48000 D/SMAO-2 15200 (2200) 80 90 179.1 22391 — 100.0.  0.0 25,161 5 418D/SMAO-2 15200 (2200) 65 30 40.5 96770 — 83.2 16.8 3,442 6 — B/SMAO-21380 (200) 80 — — — — — — — 7 — F/I  903 (131) 85 60 75.5 35322 106691.7 8.3 — 8 — F/I  924 (134) 85 15 15.5 53852 1661 91.7 7.7 — 9 —C/SMAO  917 (133) 85 60 145.4 53874 2083 92.5 4.7 — 10 — B/SMAO  896(130) 85 60 36.9 20595 650 92.0 7.0 — 11 — B/SMAO 1410 (205) 80 60 56.832529 1030 89.1 10.0 — 12 — B/SMAO 676 (98) 80 60 31.9 19195 607 — — 13— E/SMAO  924 (134) 85 30 1.04 561 43.3 — — 14 — E/SMAO  945 (137) 85 301.22 341 26.2 — — 15 — A/SMAO  951 (138) 85 30 158.6 77096 2966 — —

These data show the catalyst compounds, catalyst systems, andpolymerization processes disclosed herein can produce polymers havingimproved properties, such as high polymer melting point, high polymermolecular weights, an increased conversion and/or comonomerincorporation, which may further include a significant amount of vinyltermination.

The catalysts, in an embodiment according to the invention, provideimprovement in catalyst activity, produce polymers with improvedproperties or both. Crystallographic techniques indicate that theappended ring system or systems (e.g., the carbazole ring systems) areoriented transversely, e.g., perpendicular, to the phenol rings. Thesecatalysts have a structure to provide a broad corridor for the polymerylmoiety to reside and for the monomer to insert during the polymerizationprocess. As such, catalysts according to one embodiment of the instantdisclosure provide for an ability to control one or more characteristicsof polymerization, tacticity, comonomer insertion, and the like.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text, provided however that anypriority document not named in the initially filed application or filingdocuments is NOT incorporated by reference herein. As is apparent fromthe foregoing general description and the specific embodiments accordingto the invention, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including” for purposes ofAustralian law. Likewise whenever a composition, an element or a groupof elements is preceded with the transitional phrase “comprising”, it isunderstood that we also contemplate the same composition or group ofelements with transitional phrases “consisting essentially of,”“consisting of”, “selected from the group of consisting of,” or “is”preceding the recitation of the composition, element, or elements andvice versa.

What is claimed is:
 1. A polyolefin, comprising: i) at least 50 mole %ethylene; ii) a ratio of saturated chain ends to allyl chain ends ofgreater than 1:1; iii) a ratio of allylic vinyl groups per molecule asdetermined by ¹³C NMR of at least 50%; iv) an Mw of 5,000 to 1,000,000g/mol as determined by ¹H NMR; v) an allylic vinyl content of at least50 mole %, based upon total number of moles of unsaturation, asdetermined by ¹H NMR; and vi) a ratio of long chain branching, of atleast 7 carbons, of greater than 0.5 per 1000 carbon atoms, asdetermined according to ¹³C NMR.
 2. The polyolefin of claim 1, whereinthe polyolefin is produced by a process comprising: contacting one ormore olefins with a catalyst system at a temperature, a pressure, andfor a period of time sufficient to produce a polyolefin, the catalystsystem comprising an activator and a catalyst compound disposed on asupport; and the catalyst compound is according to Formula I, FormulaII, Formula III, or a combination thereof: Formula I being representedby:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 4, 5 or 6 transition metal; N¹, N²,N³ and N⁴ are nitrogen; O is oxygen; each of X¹ and X² is,independently, a univalent C₁ to C₂₀ hydrocarbyl radical, a functionalgroup comprising elements from Groups 13-17 of the periodic table of theelements, or X¹ and X² join together to form a C₄ to C₆₂ cyclic orpolycyclic ring structure; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, R²², R²³, R²⁴,R²⁵, R²⁶, R²⁷, and R²⁸ is, independently, a hydrogen, a C₁-C₄₀hydrocarbyl radical, a functional group comprising elements from Groups13-17 of the periodic table of the elements, or two or more of R¹ to R²⁸may independently join together to form a C₄ to C₆₂ cyclic or polycyclicring structure, or a combination thereof; and Y is a divalent C₁ to C₂₀hydrocarbyl; Formula II being represented by:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 4, 5 or 6 transition metal; N¹, N²and N³ are nitrogen; O is oxygen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, and R²¹ is, independently, ahydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group comprisingelements from Group 13-17 of the periodic table of the elements, or twoor more of R¹ to R²¹ may independently join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, or a combination thereof; subjectto the proviso that R¹⁹ is not a carbazole or a substituted carbazoleradical, and Y is a divalent C₁ to C₂₀ hydrocarbyl radical; Formula IIIbeing represented by:

wherein each solid line represents a covalent bond and each dashed linerepresents a bond having varying degrees of covalency and a varyingdegree of coordination; M is a Group 4, 5 or 6 transition metal; N¹ andN² are nitrogen; O is oxygen; each of X¹ and X² is, independently, aunivalent C₁ to C₂₀ hydrocarbyl radical, a functional group comprisingelements from Groups 13-17 of the periodic table of the elements, or X¹and X² join together to form a C₄ to C₆₂ cyclic or polycyclic ringstructure; each R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, R²⁰, R²¹, and R²² is, independently, ahydrogen, a C₁-C₄₀ hydrocarbyl radical, a functional group comprisingelements from Group 13-17 of the periodic table of the elements, or twoor more of R¹ to R²² may independently join together to form a C₄ to C₆₂cyclic or polycyclic ring structure, or a combination thereof; at leastone of R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷, R¹⁸, R¹⁹, or R²⁰ comprisefluorine; and Y is a divalent C₁ to C₂₀ hydrocarbyl radical.
 3. Thepolyolefin of claim 1, comprising at least 99.9 mole percent ethylene.4. The polyolefin of claim 1, wherein the ratio of allylic vinyl groupsper molecule is at least 80%.
 5. The polyolefin of claim 1, furthercomprising propylene.
 6. The polyolefin of claim 1, comprising anallylic vinyl content of at least 80 mole %, based upon total number ofmoles of unsaturated groups.
 7. The polyolefin of claim 1, comprising anumber average molecular weight (M_(e)) from 1250 g/mol into 100,000g/mol.
 8. The polyolefin of claim 1, comprising a ratio of long chainbranching, of at least 7 carbons, of greater than 1 per 1000 carbonatoms, as determined according to ¹³C NMR.
 9. A polyolefin, comprising:i) at least 50 mole % ethylene; ii) a ratio of saturated chain ends toallyl chain ends of greater than 1:1 and a ratio of methyl chain ends tovinyl chain ends from 1:1 to 4:1; iii) a ratio of allylic vinyl groupsper molecule as determined by ¹³C NMR of at least 50%; iv) an Mw of5,000 to 1,000,000 g/mol as determined by ¹H NMR; v) an allylic vinylcontent of at least 50 mole %, based upon total number of moles ofunsaturation, as determined by ¹H NMR; and vi) a ratio of long chainbranching, of at least 7 carbons, of greater than 0.5 per 1000 carbonatoms, as determined according to ¹³C NMR.
 10. The polyolefin of claim1, comprising a ratio of methyl chain ends to vinyl chain ends from 1:1to 3:1.
 11. The polyolefin of claim 1, wherein at least 80 wt % of thepolyolefin has one allylic vinyl group per molecule.
 12. The polyolefinof claim 1, wherein at least 95 wt % of the polyolefin has one allylicvinyl group per molecule.
 13. The polyolefin of claim 1, comprising aweight average molecular weight (M_(w)) of 50,000 to 500,000 g/mol. 14.The polyolefin of claim 1, comprising an Mw/Mn of from greater than 1 to4.
 15. The polyolefin of claim 2, wherein the catalyst compound isaccording to Formula I.
 16. The polyolefin of claim 2, wherein thecatalyst compound is according to Formula II.
 17. The polyolefin ofclaim 2, wherein the catalyst compound is according to Formula III. 18.A polyolefin, comprising: i) at least 95 mole % ethylene; ii) a ratio ofsaturated chain ends to allylic vinyl chain ends of 1:1 to 3:1; iii) aratio of allylic vinyl groups per molecule as determined by ¹³C NMR ofat least 50%; iv) an Mw of 5,000 to 1,000,000 g/mol as determined by ¹HNMR; v) at least 80 mole % allylic vinyl chain ends, based upon totalmoles of unsaturation, as determined by ¹H NMR; vi) an Mw/Mn of fromgreater than 1 to 4; vii) a ratio of long chain branching, of at least 7carbons, of greater than 0.5 per 1000 carbon atoms, as determinedaccording to ¹³C NMR.
 19. The polyolefin of claim 18, wherein thepolyolefin is produced by a process comprising contacting one or moreolefins with a catalyst system at a temperature, a pressure, and for aperiod of time sufficient to produce the polyolefin, wherein thecatalyst system comprises an activator and a salan catalyst precursorcompound disposed on a support.
 20. The polyolefin of claim 18,comprising at least 99.9 mole percent ethylene, a ratio of allylic vinylgroups per molecule as determined by ¹³C NMR of at least 0.9, a ratio oflong chain branching of at least 7 carbons of greater than 1 long chainbranch per 1000 carbon atoms, as determined according to ¹³C NMR, and anMw from 25,000 to 750,000.